CA2279864C - Organic electrolytic cell - Google Patents
Organic electrolytic cell Download PDFInfo
- Publication number
- CA2279864C CA2279864C CA002279864A CA2279864A CA2279864C CA 2279864 C CA2279864 C CA 2279864C CA 002279864 A CA002279864 A CA 002279864A CA 2279864 A CA2279864 A CA 2279864A CA 2279864 C CA2279864 C CA 2279864C
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- positive electrode
- negative electrode
- lithium ion
- cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 197
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 105
- 229910001416 lithium ion Inorganic materials 0.000 claims description 105
- 239000011149 active material Substances 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- -1 phenol compound Chemical class 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 229920003026 Acene Polymers 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 2
- 239000007859 condensation product Substances 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- 239000007769 metal material Substances 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 210
- 239000011888 foil Substances 0.000 description 28
- 239000010935 stainless steel Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000004020 conductor Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001091 LixCoO2 Inorganic materials 0.000 description 2
- 229910015867 LixMyOz Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 210000000352 storage cell Anatomy 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical class OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910014451 C6Li Inorganic materials 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004202 carbamide Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000005352 hydroxybiphenyls Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
An organic electrolytic battery having a positive electrode, a negative electrode, and an aprotic organic solvent solution of lithium salt as an electrolyte solution. Each of a positive electrode collector and a negative electrode collector has hole penetrating front and back surfaces thereof. A negative electrode active material is capable of reversibly carrying lithium. Lithium derived from the negative electrode is carried by electrochemical contact with lithium arranged to face the negative electrode or the positive electrode. The facing area of lithium is not more than 40 % of the area of the negative electrode.
Description
ORGANIC ELECTROLYTIC CELL
Technical Field The present invention relates to an organic electrolytic cell, which has a high capacity and high voltage and is superior in charge and discharge characteristics and safety.
Background Art In recent years, a secondary cell wherein an electrically conductive polymer, an oxide of a transition metal or the like is used as the positive electrode, and metallic lithium or a lithium alloy is used as the negative electrode has been proposed as a cell to be used in place of Ni-Cd storage cells and lead storage cells, because of its high energy density.
However, when such a secondary cell is subjected to repeated charge and discharge, its capacity is largely lowered due to deterioration of the positive or negative electrode, and thus there still remains a problem in its practical aspect. Particularly by deterioration of the negative electrode, mossy lithium metal, called dendrites, are formed, and through repeated charge and discharge, the dendrites finally pierce the separator and cause a short circuit. In some case, the cell is broken and thus there has been a problem in safety, too.
Technical Field The present invention relates to an organic electrolytic cell, which has a high capacity and high voltage and is superior in charge and discharge characteristics and safety.
Background Art In recent years, a secondary cell wherein an electrically conductive polymer, an oxide of a transition metal or the like is used as the positive electrode, and metallic lithium or a lithium alloy is used as the negative electrode has been proposed as a cell to be used in place of Ni-Cd storage cells and lead storage cells, because of its high energy density.
However, when such a secondary cell is subjected to repeated charge and discharge, its capacity is largely lowered due to deterioration of the positive or negative electrode, and thus there still remains a problem in its practical aspect. Particularly by deterioration of the negative electrode, mossy lithium metal, called dendrites, are formed, and through repeated charge and discharge, the dendrites finally pierce the separator and cause a short circuit. In some case, the cell is broken and thus there has been a problem in safety, too.
To solve the above problems, there has been proposed a cell wherein a carbon material such as graphite is used as the negative electrode and a lithium-containing metallic oxide such as LiCo02 is used as the positive electrode. This cell is a so-called rocking chair-type cell wherein, after assembly of the cell, lithium ion is supplied from the lithium-containing metallic oxide as the positive electrode to the negative electrode through charge, and lithium ion of the negative electrode is returned to the positive electrode through discharge. Although the cell is characterized by a high voltage and high capacity, the high energy density as an advantage of the lithium cells has not been obtained.
In the above rocking chair-type cell, it is an essential feature to use the lithium-containing metallic oxide as the positive electrode. Therefore, when using metallic oxides (e.g. V205, Mn02, TiS2, etc.), metallic sulfides, electrically conductive polymers (e.g. polyacene organic semiconductor, etc.) or the like proposed as the positive electrode material for lithium secondary cells, it is necessary to previously carry lithium on the positive or negative electrode. To obtain these positive electrode materials, there is required a method of carrying lithium, practically and simply.
In the above rocking chair-type cell, it is an essential feature to use the lithium-containing metallic oxide as the positive electrode. Therefore, when using metallic oxides (e.g. V205, Mn02, TiS2, etc.), metallic sulfides, electrically conductive polymers (e.g. polyacene organic semiconductor, etc.) or the like proposed as the positive electrode material for lithium secondary cells, it is necessary to previously carry lithium on the positive or negative electrode. To obtain these positive electrode materials, there is required a method of carrying lithium, practically and simply.
In recent years, with the rapid progress of a study about a negative electrode material capable of reversibly carrying lithium, a material capable of carrying lithium ion in the amount exceeding that of C6Li, which is a theoretic amount of the carbon material, and an oxide such as Sn02 and Si02 have been proposed as the negative electrode material for high-capacity lithium ion secondary cells.
Among them, an infusible and insoluble substrate having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substrate being a heat-treated product of an aromatic condensation polymer, is capable of doping with lithium ion up to C2Li (Synthetic Metals, 73 (1995) P273). However, the above locking chair-type cell wherein this infusible and insoluble substrate is used as the negative electrode and the lithium-containing metallic oxide as the positive electrode can attain a capacity higher than that in the case of the carbon material after assembly, but there still remains an unsatisfactory respect in its capacity.
To solve the above problems, PCT Publication No. W095/8852, whose application was filed by the present applicant, has proposed an organic electrolytic cell comprising a positive electrode, a negative electrode and a solution of lithium salt in an aprotic organic solvent as an electrolytic solution, wherein the positive electrode contains a metallic oxide, the negative electrode is an infusible and insoluble substrate having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substrate being a heat-treated product of an aromatic condensation polymer, and the total amount of lithium ion in the cell is not less than 500 mAh/g and the amount of lithium originating in the negative electrode is not less than 100 mAh/g, based on the infusible and insoluble substrate as the negative electrode. Although this cell can attain a high capacity, a method of carrying lithium ion originating in the negative electrode, practically and simply, is required in the case of assembly of a practical cell such as cylindrical-type cell. Various specific methods thereof are proposed in Japanese Patent Kokai (Laid-Open) Publication Nos. 162159/1996, 162160/1996, 162161/1996 and 255633/1996. However, any of these methods has a problem in uniformity and operating property and the problem has still to be completely solved at present. That is, a most simple method in these specific methods includes a method of attaching a lithium metal on a positive or negative electrode, inserting the resultant into a cell container, together with the positive or negative electrode and a separator, pouring an electrolytic solution and allowing to stand, thereby to carry lithium ion on the positive or negative electrode. However, this method had such a problem that, since a lower limit of the thickness of a lithium metal foil to be attached, which can be mass-produced, is about 30 um, the thickness of the positive and/or negative electrodes increases thereby to restrict design of the cell and to exert an influence particularly on charge and discharge characteristics.
The present inventors have studied intensively in light of the problems described above, thus completing the present invention. An object of the present invention is to provide an organic electrolytic cell, which is easy to produce, and which has a high capacity and high voltage and is superior in charge and discharge characteristics and safety.
Among them, an infusible and insoluble substrate having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substrate being a heat-treated product of an aromatic condensation polymer, is capable of doping with lithium ion up to C2Li (Synthetic Metals, 73 (1995) P273). However, the above locking chair-type cell wherein this infusible and insoluble substrate is used as the negative electrode and the lithium-containing metallic oxide as the positive electrode can attain a capacity higher than that in the case of the carbon material after assembly, but there still remains an unsatisfactory respect in its capacity.
To solve the above problems, PCT Publication No. W095/8852, whose application was filed by the present applicant, has proposed an organic electrolytic cell comprising a positive electrode, a negative electrode and a solution of lithium salt in an aprotic organic solvent as an electrolytic solution, wherein the positive electrode contains a metallic oxide, the negative electrode is an infusible and insoluble substrate having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substrate being a heat-treated product of an aromatic condensation polymer, and the total amount of lithium ion in the cell is not less than 500 mAh/g and the amount of lithium originating in the negative electrode is not less than 100 mAh/g, based on the infusible and insoluble substrate as the negative electrode. Although this cell can attain a high capacity, a method of carrying lithium ion originating in the negative electrode, practically and simply, is required in the case of assembly of a practical cell such as cylindrical-type cell. Various specific methods thereof are proposed in Japanese Patent Kokai (Laid-Open) Publication Nos. 162159/1996, 162160/1996, 162161/1996 and 255633/1996. However, any of these methods has a problem in uniformity and operating property and the problem has still to be completely solved at present. That is, a most simple method in these specific methods includes a method of attaching a lithium metal on a positive or negative electrode, inserting the resultant into a cell container, together with the positive or negative electrode and a separator, pouring an electrolytic solution and allowing to stand, thereby to carry lithium ion on the positive or negative electrode. However, this method had such a problem that, since a lower limit of the thickness of a lithium metal foil to be attached, which can be mass-produced, is about 30 um, the thickness of the positive and/or negative electrodes increases thereby to restrict design of the cell and to exert an influence particularly on charge and discharge characteristics.
The present inventors have studied intensively in light of the problems described above, thus completing the present invention. An object of the present invention is to provide an organic electrolytic cell, which is easy to produce, and which has a high capacity and high voltage and is superior in charge and discharge characteristics and safety.
5 Still other objects, features and advantages of the present invention will become apparent from the following description.
Disclosure of the Invention To attain these objects, the organic electrolytic cell of the present invention has the following construction.
That is, aspect 1 of the present invention provides an organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the negative electrode capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which a plurality of positive electrode plates, separators and negative electrode plates are laminated in sequence or a wound structure, wherein the lithium ion originating in the negative electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the negative electrode.
Aspect 2 of the present invention provides an organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the positive electrode and an active material of the negative electrode, each capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which a plurality of positive electrode plates, separators and negative electrode plates are laminated in sequence or a wound structure, wherein at least one portion of the lithium ion originating in the positive electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the positive electrode.
Brief Description of the Drawings FIG. 1 is a view illustrating the arrangement of a first embodiment of electrodes in the cell according to the present invention.
FIG. 2 is a view illustrating the arrangement of a second embodiment of electrodes in the cell according to the present invention.
FIG. 3 is a view illustrating the arrangement of a third embodiment of electrodes in the cell according to the present invention.
FIG. 4 is a view illustrating the arrangement of a fourth embodiment of electrodes in the cell according to the present invention.
FIG. 5 is a view illustrating the arrangement of a fifth embodiment of electrodes in the cell according to the present invention.
FIG. 6 is a view illustrating the arrangement of a sixth embodiment of electrodes in the cell according to the present invention.
FIG. 7 is a view illustrating the arrangement of a seventh embodiment of electrodes in the cell according to 7a the present invention.
FIG. 8 is a view illustrating the arrangement of an eighth embodiment of electrodes in the cell according to the present invention.
FIG. 9 is a view illustrating the arrangement of a ninth embodiment of electrodes in the cell according to the present invention.
Best Mode for Carrying Out the Invention The active material of the negative electrode in the organic electrolytic cell of the present invention may be any one capable of reversibly carrying lithium ion, and examples thereof include graphite, various carbon materials, polyacene substance, tin oxide, silicon oxide and the like.
Among them, it is preferred to use an infusible and insoluble substance having a polyacene skeletal structure and a -772?~4-4 $
hydrogen/carbon atomic ratio of 0.50 to 0.05, the substance being a heat-treated product of an aromatic condensation polymer, because a high capacity can be obtained.
The aromatic condensation polymer is a condensate of an aromatic hydrocarbon compound and aldehydes. As the aromatic hydrocarbon compound, for example, so-called phenols such as phenol, cresol, xylenol and the like can be suitably used. There can also be used methylenebisphenols represented by the following formula:
-CH CF-I 3) ~ 3}x 2 Y
wherein x and y are independently 0, 1 or 2, or hydroxybiphenyls or hydroxynaphthalenes. For practical purpose, phenols, particularly phenol, are preferred.
As the aromatic condensation polymer, there can also be used a modified aromatic condensation polymer wherein a portion of the aromatic hydrocarbon compound having phenolic hydroxyl groups is replaced with an aromatic hydrocarbon compound having no phenolic hydroxyl group such.
as xylene, toluene or aniline, for example,.a condensate of phenol,xylene and formaldehyde. Furthermore, there can also be used a modified aromatic polymer wherein the above portion is replaced with melamine or urea. A furan resin 772,14-4 is also preferred.
As the aldehyde, it is possible to use aldehydes such as formaldehyde, acetaldehyde and. furfural, but.
formaldehyde- is preferred. A pheno.lformaldehyde condensate- may be any of a novolak type, a resol type or a mixture thereof.
The infusible and insoluble substance can be obtained by a heat treatment of the above aromatic polymer, and includes all of infusible and insoluble substances having a polyacene skeletal structure described in Japanese'Patent Publication Nos. 44212/19S9 and 24024/1991.
The infusible and insoluble substance used in the present invention can. also be produced as follows . That is, an infusible and insoluble substance having a hydrogen/ca=bon atomic ratio (hereinafter referred to as:
H/C) of 0. 50 to 0. 05, pref erably 0. 35 to 0=.10 can be obtained by gradually heating the aromatic condensa=Cion polymer up to -a proper temperature of 400 to 800r, in 'a non-oxidizing atmosphere (including a vacuum).
It is also -possible to obtein an infusible and insoluble- substance having a specific surface area, measured by the. BET method, of not'less than 600 m2/g according to the method described in Japanese. Patent Publication No. 24024/1991. For example, an infusible and insoluble substance having the above H/C and having a specific surface area, rneasured by =the BET method, of not less than 600 m2/g can also be obtained by preparing a solution containing an initial condensate of an aromatic condensation polymer and an inorganic salt such as zinc chloride; heating the solution to cure it in a mold;
5 gradually heating the cured matter in a non-oxidizing atmosphere (including a vacuum) up to a temperature of 350 to 800 C, preferably up to a proper temperature of 400 to 750 C; and then sufficiently washing it with water, diluted hydrochloric acid or the like.
10 With respect to the infusible and insoluble substance used in the present invention, according to X-ray diffraction (CuKa), the main peak is observed at 2e=24 or less, and besides another peak is observed at between 28=41 and 2e=46 , in addition to the main peak. Namely, it is suggested that the infusible and insoluble substrate has a polyacene skeletal structure wherein an aromatic polycyclic structure is moderately developed, and takes an amorphous structure. Thus the substrate can be doped stably with lithium ion and, therefore, it is useful as an active material for cells.
It is preferred that this infusible and insoluble substance has H/C ranging from 0.50 to 0.05. When H/C
exceeds 0.50, the aromatic polycyclic structure does not sufficiently develop, and thus it is impossible to conduct doping and undoping of lithium ion smoothly, and when a cell is assembled, charge and discharge efficiency is lowered.
On the other hand, when H/C is less than 0.05, the capacity "of the cell of the present invention is likely to be lowered.
The negative electrode in the organic electrolytic cell according to the present invention is cam:posed of the above infusible and insoluble substance (herein'after referred to as P+AS), and practically, it is preferred.to use a form obtained by forming PAS in an easily formable form such as a powdery form, a granular form or a short fiber form with a binder. As the binder, there can be used fluorine-containing resins such, as polyethylene tetrafluoride and polyvinylidene fluoride, and thermoplastic resins such as polypropylene and polyethylene.
It is preferred to use a fluorine binder. Use of a fluorine binder having a fluorine/carbon atomic ratio (herei.nafter referred to as F/C) of less than 1.5 and not less than 0'. 75 is preferred, and use of a-fluorine binder havi.ng a fluorine/carbon atomic ratio of less than 1.3 and not less than 0.75 is more preferred.
The fluorine binder includes, for example, 20. polyvinylidene fluoride, vinylidene fluoride-ethylene trifluoride copolymer,, ethylene-ethylene tetrafluoride copolymer, propylene-ethylene tetrafluoride or the like.
Furthermore, it is also possible to use a fluorine-containing polymer wherein hydrogens at the principal chain are replaced with alkyl groups. In the case of the polyvinylidene fluoride, F/C is 1. In the case of.the vinylidene fluoride-ethylene trifluoride copolymer, when the molar fractions of vinylidene fluoride are 50% and 80%, F/C values become 1.25 and 1.10, respectively. In the case of the propylene-ethylene tetrafluoride copolymer, when the molar fraction of propylene is 50%, F/C becomes 0.75.
Among them, polyvinylidene fluoride, and a vinylidene fluoride-ethylene trifluoride copolymer wherein the molar fraction of vinylidene fluoride is not less than 50% are preferred. For practical purpose, polyvinylidene fluoride is preferred.
When using these binders, it is possible to sufficiently utilize the doping ability (capacity) with lithium ion which PAS has.
When using PAS, oxide or the like as the active material of negative electrode, if necessary, electrically conductive materials such as acetylene black, graphite, metallic powder and the like may be appropriately added in the negative electrode of the organic electrolytic cell of the present invention.
The active material of positive electrode in the organic electrolytic cell according to aspect 1 of the present invention is not specifically limited, for example there can be used lithium-containing metallic oxides capable of electrochemically doping with lithium ion and electrochemically undoping lithium ion, which can be represented by the general formula LixMyOz (M is a metal, or can be two or more metals) such as LixCo02, LixNi02, LixMn02 or LixFe02r or oxides of transition metals such as cobalt, manganese and nickel. The above electrically conductive polymers such as PAS can also be suitably used.
Particularly, when a high voltage and high capacity are required, a lithium-containing oxide having a voltage of not less than 4 V vs lithium metal is preferred. Among them, lithium-containing cobalt oxides, lithium-containing nickel oxides or lithium-containing cobalt-nickel double oxides are particularly preferred.
The active material of positive electrode in the organic electrolytic cell according to aspect 2 of the present invention is not specifically limited, for example there can be used lithium-containing metallic oxides capable of reversibly carrying lithium ion, which can be represented by the general formula LixMyOz (wherein M is a metal, or can be two or more metals and x, y and z are each a positive number) such as LixCo02, LixNi02, LixMn02 or LixFe02r or oxides and sulfides of transition metals such as cobalt, manganese, vanadium, titanium and nickel. The above electrically conductive polymers such as PAS can be suitably used. These active materials of positive electrode can be roughly classified into two kinds. That is, they are an active material of positive electrode (referred to as a first type of an active material of positive electrode in the present invention) capable of emitting lithium ion through electrochemical oxidation, namely charge, 7721,4-4 such as lithium-containing cobalt oxides, litYaium-containing nickel oxides and lithium-containing cobalt-nickel double oxides, and the other active material of.
positive electrode (referred to as a second type of an active material of positive electrode in the present inven tion) .
Particularly, when a high voltage is required, a lithium-containing oxide having a voltage of 'not: less than 4 V vs lithium metal is preferred. Among them, lithium-containing cobalt oxides, lithium-containing=nickel oxides or lithium-containing cobalt-nickel double oxides are particularly preferred.
The positive electrode in the organic electrolytic cell of the present invention is one made by optionally adding;an electrically conductive material and a binder to the above active material and molding the mixture, and the kind and composition of the electrically conductive material and binder can be, appropri.ately specified.
As the electrically conductive material, a powder of a metal such as metallic nickel can be used. Carbon material such as active carbon, carbon black, acetylene black and graphite can be suitably used. A mixing ratio of these electrically conductive materials varies depending on the "electric conductivity of the active material, shape of the electrode, etc. , but it is suitable to add it in an amount of 2 to 40* based on the active material. .
The binder may be any one which is insoluble in-an electrolytic solution described hereinafter used in the organic electrolytic solution of the present invention.
There can be preferably used, for example, rubber binders such as SBR, fluorine-containing resins such as polyethylene tetrafluoride and polyvinylidene fluoride, and thermoplastic resins such as polypropylene and polyethylene. The mixing ratio is preferably not more than 20% based on the above active material.
As the solvent constituting the electrolytic solution used in the organic electrolytic solution of the present invention, an aprotic organic solvent is used. The aprotic organic solvent includes, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, 7 -butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane or the like. Furthermore, a mixed solution of two or more of these aprotic organic solvents can also be used.
Furthermore, as an electrolyte to be dissolved in the single or mixed solvent, any of electrolyte capable of forming lithium ions can be used. The electrolyte includes, for example, LiI, LiClO4 , LiAsFb , LiBF4 , LiPFb or the like.
The electrolyte and solvent are mixed in a state of being sufficiently dehydrated to give an electrolytic solution. To make the internal resistance by the electrolytic solution small, it is preferred to make the concentration of the electrolyte in the electrolytic solution at least 0.1 mol/1 and it is more preferred to make it 0.2 to 1.5 mol/l.
The current collector of positive electrode and current collector of negative electrode in the organic electrolytic cell of the present invention are each provided with pores piercing from a front surface to a back surface, and are made of materials such as expanded metal, punched metal, net, foamed material or the like. The form and number of these through pores are not specifically limited and can be appropriately determined so that lithium ions in the electrolytic solution described hereinafter can transfer between the front and back surfaces of the electrode without being interrupted by the current collectors of electrodes.
For example, when the proportion (form and number) of the through pores is determined by the porosity of the electrode-current collector, it is preferred to make the porosity 10% or more, particularly 30% or more. The porosity of the electrode current collector is obtained by reducing a ratio of {1 - (weight of current collector/true specific gravity of current collector)/(apparent volume of current collector)} to percentage. When this porosity is small, the time of carrying lithium ion originating in the negative or positive electrode becomes long. On the other hand, when it is too large, the resulting cell has a high internal resistance and, therefore, the porosity is preferably determined by considering the desired cell characteristics, thickness of the electrode, safety, and kind of the current collector. As the material of the electrode-current collector, there can be used various materials which are generally proposed in lithium cells.
Aluminum and stainless steel can be used as the current collector of positive electrode, whereas, stainless steel, copper and nickel can be used as the current collector of negative electrode. With respect to the current collector of positive electrode of the organic electrolytic cell according to aspect 2, when lithium metal is directly attached as described hereinafter, it is preferred to use a material, which does not make an alloy with lithium metal and has resistance to electrochemical oxidation, such as stainless steel.
In the organic electrolytic cell according to aspect 1 of the present invention, lithium ion originating in the negative electrode is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode and the opposed area of the lithium metal is not more than 40%, preferably not more than 30% of the area of the negative electrode. In the organic electrolytic cell according to aspect 2 of the present invention, lithium ion originating in the positive electrode is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode and the opposed area of the lithium metal is not more than 40%, preferably not more than 30% of the area of the positive electrode. The term "lithium metal" used in this specification refer to any material, which contains at least lithium and is capable of supplying lithium ions, such as lithium metal, lithium-aluminum alloy or the like.
In the case of a metallic lithium foil or metallic lithium plate, the opposed area of lithium metal is an area at the portion where the foil or plate and the negative or positive electrode are faced each other. That is, in the case of those having the form shown in FIG. 1, FIG. 2, FIG. 4 and FIG. 5 to be described hereinafter as embodiments of the present invention, it is an area of one surface. In the case of those having the form shown in FIG. 3 and FIG. 6, it is the total of areas of both surfaces. In the case of lithium metal formed in a cylindrical or prismatic shape, it is an area of the side. Any of the area of negative electrode and area of positive electrode is an area at the portion where the negative electrode and positive electrode are faced each other.
When a lithium metallic foil is attached on both surfaces of a negative electrode plate molded on both surfaces of a copper foil, the opposed area of lithium metal becomes 100% of the area of negative electrode. When a lithium metallic foil is attached on one surface of a negative electrode plate molded into an expanded metal, the opposed area of lithium metal becomes 50% of the area of negative electrode.
When a lithium metallic foil is attached on both surfaces of a positive electrode plate molded on both surfaces of an aluminum foil, the opposed area of lithium metal becomes 100% of the area of positive electrode. When a lithium metallic foil is attached on one surface of a positive electrode plate molded into an expanded metal, the opposed area of lithium metal becomes 50% of the area of positive electrode.
In the organic electrolytic cell according to the present invention, by locally arranging lithium ion originating in the negative or positive electrode at a specific position, the opposed area of lithium metal is made 40% or less, preferably 30% or less of the area of negative electrode or area of positive electrode, thereby making it possible to improve the freedom of the cell design and mass-productivity and to afford excellent charge and discharge characteristics. That is, it is very complicated to attach a lithium metal on almost all of the negative or positive electrode, like the above example, and it is not suited for industrial production and it becomes difficult to conduct mass-production. When the opposed area of lithium metal exceeds 40% of the area of negative electrode or area of positive electrode, the thickness of the electrode is decided by that of lithium metal, thereby to cause a problem that desired charge and discharge characteristics can not be obtained.
In the organic electrolytic cell according to aspect 1 of the present invention, the total amount of lithium ion contained the cell is preferably not less than 500 mAh/g and the amount of lithium ion originating in the negative electrode is preferably not less than 100 mAh/g, based on the active material of negative electrode. The total amount of lithium ion contained the cell is the total of the amount of lithium ion originating in the positive electrode, that of lithium ion originating in the electrolytic solution and that of lithium ion originating in 5 the negative electrode. Lithium ion originating in the positive electrode is lithium ion contained in the positive electrode on assembly of the cell, and a portion or all of the lithium ion is supplied to the negative electrode through an operation of applying a current from an external 10 circuit (charge).
In the organic electrolytic cell according to aspect 2 of the present invention, lithium ion originating in the positive electrode is lithium ion contained in the positive electrode and at least one portion, namely a 15 portion or all of lithium ion is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode. For example, when using LiCo02 as the active material of positive electrode, LiCoO2 has already contained lithium ion on assembly of the cell, but lithium 20 ion originating in the positive electrode is obtained by further adding lithium ion carried through electrochemical contact with lithium metal. On the other hand, when using V205 as the active material of positive electrode, since this material does not contain lithium ion, all of lithium ion originating in the positive electrode is carried by electrochemical contact with lithium metal. At least one portion, namely portion or all of this lithium ion originating in the positive electrode is supplied to the negative electrode through an operation of applying a current from an external circuit (charge). Then, the electrochemical contact between lithium metal and the positive electrode initiates when the electrolytic solution is poured into the cell system. When using the above first type of an active material of positive electrode, since said active material of positive electrode has already contained releasable lithium ion, it becomes possible to charge the cell system immediately after pouring the electrolytic solution into the cell system. Also when using the second type of an active material of positive electrode, it is possible to charge the cell system before all lithium ion is completely charged on the active material of positive electrode after pouring the electrolytic solution into the cell system. The above charge operation is effective to reduce the carrying time and to prevent the positive electrode from being in an over-discharge state, thereby preventing deterioration of the positive electrode due to the carrying operation of lithium ion.
Lithium ion originating in the electrolytic solution in the organic electrolytic cell of the present invention is lithium ion in the electrolytic solution contained in the separator, positive electrode and negative electrode, whereas, lithium ion originating in the negative electrode is lithium ion carried on the active material of negative electrode and is lithium ion other than lithium ion originating in the positive electrode and lithium ion originating in electrolytic solution.
FIG. 1 to FIG. 6 each illustrate an embodiment of a cell of the type wherein plural pairs of positive electrode plates, a separator and a negative electrode plate are laminated in sequence in the organic electrolytic cell of the present invention.
FIG. 1 illustrates one embodiment of the arrangement of electrodes in a casing of the cell of the above type. In this embodiment, a negative electrode 2 molded on both surfaces of a current collector 2' of negative electrode and a lithium metal 4 contact-bonded on a lithium metal current collector 4' made of a stainless mesh or a copper expanded metal, which is arranged at the lower portion of a multi-layer unit, are connected through a conductor 5. A positive electrode 1 molded on both surfaces of a current collector 1' of positive electrode is laminated via the above negative electrode 2 and separator 3, and is connected through a conductor 5'. The above current collector 2' of negative electrode and lithium metal current collector 4' can also be welded directly.
FIG. 2 illustrates a modified embodiment of the arrangement of electrodes shown in FIG. 1. In this cell, the lithium metal 4 contact-bonded on the lithium metal current collector 4' is arranged at the upper and lower portions of the multi-layer unit, respectively.
Another modified embodiment shown in FIG. 3 illustrates that the lithium metal 4 is arranged in the center of the multi-layer unit.
FIG. 4 illustrates another embodiment _of the arrangement of. electrodes of the above type. In this embodiment, the positive electrode 1 molded on both surfaces of the current collector 1' of positive electrode and the lithium metal 4 contact-bonded on the lithium metal current collector 4' made of a stainless mesh or a copper expanded metal, which is arranged at the lower portion of the multi - layer unit, are connected through the conductor 5'.
The negative electrode 2 molded.on both surfaces of the current collector 2' of negative electrode is laminated via .
the above positive electrode 1 and separator 3, and is connected through the conductor 5. The above current collector 1' of positive electrode and lithium metal current collector 4' can also be welded directly:
FIG. 5 illustrates a modified einbodiment of the arrangement of electrodes shown in FIG. 4. In this cell, the lithium metal 4 contact-bonded on the lithium metal current collector 4' is arranged at the upper and lower portions of the multi-layer unit, respectively.
Another modified embodiment shown in FIG. 6 illustrates that the lithium metal 4 is.arranged in the center of the multi-layer unit.
In the -above respective embodiments, the .'current collector 1` of positive electrode and current collector 2' of negative electrode are each provided with pores (not shown) piercing from the front surface to the back surface, and a terminal of positive: electrode and a 1p terminal of negative electrode of the cell are connected with them,.respectively.
In the embodiments.shown in .FIG. 1 to FIG. 3, the current collector 1' of positive electrode can be directly welded without providing the conductor 5. In the embodiments shown in FIG. 4 to FIG. 6, the current collector 2' of negative electrode can be directly welded without providing the .conductor 5.
As mentioned above, in the arrangement of the.
electrodes of a multi-layer type cell, the position of the 20 lithium metal 4 to be arranged can be appropri.ately changed as shown in the above embodiments.
FIG. 7 to FIG. 9 each illustrate an embodiment of the arrangement of electrodes of a cell having a wound-type structure used in a cylindrical cell as the embodiment of the_present invention. In the arrangement of these cells; a positive.electrode 1 and a negative electrode .2 are molded on a current collector (in the drawing, the current collector is eliminated). FIG. 7 illustrates an embod.iment wherein the lithium metal 4 is attached on the current collector of an outer-most negative electrode 2 (in the drawing, only the lithium metal 4 is shown at the' portion where the lithium metal is lami.nated) , whereas, FIG. 8 illustrates an embodiment wherein the-lithium metal 4 is attached on the current collector of an outer-most positive electrode .1 ( i.n the drawing; only the -lq lithium metal 4 is shown. at the portion where the lithium metal is laminated)-.. FIG. 9 illustrates an embodiment wherein the lithium metal 4 having a columnar.shape is arranged in the center of a wound-type structure.
In the above arrangement-of the electrodes; -the separator 3 is made of a porous material, which is durable against the electrolytic solution or the electrode active material and which has open pores and is electrically non-conductive. There can be usually used a cloth., non-woven fabric or porous material made of glass fiber, 20 polyethylene or polypropylene. To decrease the internal resistance of the cell; the separator 3 is preferably as thin as possible. Its thickness, however, is determined by appropriately considering the amount of electrolytic solution held, permeability, strength or the like. The separator 3 is impregnated with the electrolytic solution, and in the electrolytic solution, the above compound capable of forming lithium ions with which doping is made is dissolved in an aprotic organic solvent. The electrolytic solution is usually a liquid and impregnated into the separator 3, but it can also be used, without any separator 3, after being made into gel or a solid for preventing leakage of the solution.
In the above embodiments, the negative or positive electrode is made contact with lithium metal (lithium metal in these embodiments) via the conductor 5 or 5' made of nickel, copper or stainless steel, or attaching lithium metal on the current collector of negative electrode or the current collector of positive electrode, but the organic electrolytic cell of the present invention is not specifically limited to this structure. For example, lithium metal may also be made contact by directly attaching it on the negative or positive electrode, or by directly attaching it on a negative electrode case or a positive electrode case. That is, it is necessary to arrange so that, when the electrolytic solution is poured on assembly of the cell, any of the negative or positive electrode is electrochemically made contact with lithium metal thereby to carry lithium ion on an active material of negative electrode or an active material of positive electrode and the active material of negative electrode via the electrolytic solution.
Particularly, by filling the pore portion of an electrically conductive porous material such as stainless steel mesh as the lithium metal current collector with 80%
or more of lithium metal, a space is hardly formed between electrodes by disappearance of lithium metal even if lithium ion is doped. Thus, lithium ion is smoothly carried on the active material of negative electrode or the active material of positive electrode.
To the contrary, there can also be employed a method of arranging lithium metal in a transverse direction of the negative electrode plate or positive electrode plate and carrying lithium ion on the active material of negative electrode or active material of positive electrode by electrochemical contact between the negative or positive electrode and lithium metal in the cell. However, according to this method, it is impossible to avoid a problem that unevenness in doping in the cell increases and lithium metal is partially deposited on the negative electrode, resulting in long carrying time. Accordingly, in the present invention, it is required to arrange so that the positive or negative electrode and lithium metal face each other.
In this cell, the amount of lithium ion originating in the negative electrode or lithium ion originating in the positive electrode can be appropriately determined by the desired cell, active material of negative electrode or active material of positive electrode, but a particularly high-capacity cell can be obtained by using PAS
a M
as the active material of negative electrode and satisfying the following conditions. That is, when using PAS as the active material of negative electrode, the total amount of lithium ion in the cell is preferably not less than 500 mAh/g, more preferably not less than 600 mAh/g, based on PAS of negative electrode so as to obtain a sufficient capacity.
In the organic electrolytic cell according to aspect 1, the amount of lithium ion originating in the negative electrode is preferably not less than 100 mAh/g, more preferably not less than 150 mAh/g, based on PAS of negative electrode. When the amount of lithium ion originating in the negative electrode is less than 100 mAh/g even if the total amount of lithium ion is not less than 500 mAh/g based on PAS of negative electrode, there is some possibility of causing a problem that a sufficient capacity can not be obtained. When using a lithium-containing metal oxide as the positive electrode, a high capacity can be obtained by adjusting the amount of lithium ion originating in the negative electrode to 600 mAh/g or less based on PAS of negative electrode, which is preferred. Although the amount of lithium ion originating in the positive electrode and that of lithium ion originating in the electrolytic solution can be appropriately determined, the amount of lithium ion originating in the positive electrode is preferably not less than 300 mAh/g based on PAS of negative electrode so as to obtain a high capacity when using a lithium-containing metal oxide as the positive electrode.
In the organic electrolytic cell according to aspect 2, when using the above first type of an active material of positive electrode, lithium ion originating in the positive electrode is preferably carried in the amount of not less than 100 mAh/g, more preferably not less than 150 mAh/g, based on PAS of negative electrode, in addition to lithium ion contained intrinsically in the positive electrode so as to obtain a high capability. In this organic electrolytic cell, lithium ion originating in the negative electrode may be previously carried on PAS as the active material of negative electrode. Particularly, when using the above second type of an active material of positive electrode, since the amount of lithium ion to be carried increases, it is effective to separately carry a required amount of lithium ion on the negative or positive electrode so as to reduce the carrying time.
The shape of the organic electrolytic cell according to the present invention includes, for example, cylindrical shape, rectangular shape and box shape, but is not specifically limited.
[Example 1]
A phenol-formaldehyde resin having a thickness of 0.5 mm was put in a silicon carbide heating element, and heat-treated by heating to 500 C under a nitrogen atmosphere at a rate of 50 C/hour and then heating to 650 C at a rate of 10- C/hour, thereby to synthesize PAS. The PAS plate thus obtained was ground by using a disc mill to obtain PAS powder having an average particle diameter of about 7Am. The H/C
ratio of this PAS powder was 0.22.
Then, 100 parts by weight of the PAS powder and 10 parts by weight of acetylene black were sufficiently mixed with a solution of 10 parts by weight of polyvinylidene fluoride powder in 120 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of a copper expanded metal having a thickness of 60 ,u m (porosity: 70%) (manufactured by Sank Co., LW: 1 mm, SW:
0. 5 mm) to obtain a PAS negative electrode having a thickness of 520 gm. In addition, 100 parts by weight of LiCoO2 (first type of positive electrode) and 5 parts by weight of graphite were sufficiently mixed with a solution of 3.5 parts by weight of polyvinylidene fluoride powder in 50 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of an aluminum expanded metal having a thickness of 240 9 m (porosity: 88%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 780 gm.
Using the above positive electrode (2.0 X 3.0 cm2), PAS negative electrode (2. 2 X 3. 2 cmz ) and a polypropylene separator having a thickness of 25 am, two cells wherein the positive electrode, separator and negative electrode (four positive electrodes) are laminated shown in FIG. 1 were assembled. As two outer negative electrodes, one having a thickness of 290 pm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (240 pm, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 3) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding.
The opposed area (7.04 cm2) of lithium metal was 12.5% of the area of the negative electrode (7.04 cm2 x 8 (both surfaces x 3, one surface x 2) = 56.32 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. As the electrolytic solution, a solution of LiPF6 at a concentration of 1 mol/l in a 1:1 (volume ratio) mixed solution of ethylene carbonate and diethyl carbonate was used. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 720 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated.
As a result, it was 300 mAh.
[Example 2]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 182 um and a positive electrode having a thickness of 271 um were obtained. Using the positive electrode (2.0 x 3.0 cmz), PAS negative electrode (2.2 x 3.2 cm2) and a polypropylene separator having a thickness of 25 1um, two cells wherein the positive electrode, separator and negative electrode (nine positive electrodes) are laminated shown in FIG. 1 were assembled.
As two outer negative electrodes, one having a thickness of 130 pm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (289 um, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (7.04 cm2) of lithium metal was 5.6% of the area of the negative electrode (7.04 cm2 x 18 (both surfaces x 8, one surface x 2) = 126.72 cm2) . The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA
until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Example 3]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine positive electrodes) are laminated shown in FIG. 1 were assembled. As two outer negative electrodes, one having a thickness of 130 Um obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (100 um, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 pm was used and two plates were arranged at the upper and lower portions of an electrode multi-layer unit so as to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (7.04 cm2 x 2 (both surfaces x 2) = 14.08 cm2) of lithium metal was 11.1%
of the area of the negative electrode (7.04 cm2 x 18 (both surfaces x 8, one surface x 2) = 126.72 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS.
One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated.
As a result, it was 620 mAh.
[Example 4]
The slurry obtained in Example 1 was molded on one 5 surface of an aluminum expanded metal having a thickness of 120 pm (porosity: 85%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 400 pm.
Using the same positive electrode, PAS negative 10 electrode and separator as in Example 1, two cells wherein the positive electrode, separator and negative electrode (four negative electrodes) are laminated shown in FIG. 4 were assembled. As two outer positive electrodes, a positive electrode having a thickness of 400 pm obtained by 15 molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 pm as described above was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (280 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 pm was used 20 and was arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 3) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2) of lithium metal 25 was 12.5% of the area of the positive electrode (6 cm2 x 8 (both surfaces x 3, one surface x 2) = 48 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V
cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 720 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 300 mAh.
[Example 5]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 4 were assembled. As two outer positive electrodes, a positive electrode having a thickness of 150 um obtained by molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 pm in the same manner as in Example 4 was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (230 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 lim was used and arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cmz) of lithium metal was 5.6% of the area of the positive electrode (6 cmZ x 18 (both surfaces x 8, one surface x 2) = 108 cm`). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 4. Also, the electrolytic solution was the same as in the above repective Examples.
The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours.
Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Example 6]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 5 were assembled. Two outer positive electrodes were the same as in Example 5. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (120 pm, 2.0 x 3.0 cm 2) on a stainless steel net having a thickness of 80 pm was used and arranged to face the positive electrode.
The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2 x 2 (both surfaces x 2) = 12 cm2) of lithium metal was 11.1% of the area of the positive electrode (6 cm2 X 18 (both surfaces x 8, one surface x 2) = 108 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 4. Also, the electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. Then, one cell was allowed to stand at room temperature for two days and decomposed.
As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Comparative Example 11 In the same manner as in Examples 1 and 4, except that an aluminum foil having a thickness of 30 pm was used as the current collector of the positive electrode and a copper foil having a thickness of 18 um was used as the current collector of the negative electrode, two kinds of cells were assembled. Each of the. celis was allowed to stand at room .temperature for 20 days, and then decomposed. As a result, almost all of lithium metal remained in both of the cells.
[Comparative Example 2]
In the sa,me manner as in Examples 1 and 4,. except that an aluminum foil having a thickness of 30 ,etm was used as the current collector of the positive electrode-, two kinds of cells were assembled. Each of the cells was allowed to stand at room temperature for 20 days, and then decomposed.
10 As a result, almost.all.of lithium metal remained in both of the cells.
[Comparative Example 3]
In the same manner as in Examples i and 4, except that a copper foil having a thickness of 18 l.Lm was used as the current collector of the negative electrode, two kinds of cells were assembled. Each of 'the cells was allowed to stand at room temperature for=20 days, and then decomposed. As a result, almost all of lithium metal remained in .both.
of the cells.
20 [Comparative Example 4]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 290 9 m and a positive electrode having a thickness of 438 9 mwere obtained. Using the positive electrode (2.0 X 3.0 cm2), PAS negative electrode (2.2 X 3.2 cm2) and polypropylene separator having a thickness of 25 gm, two cells wherein the positive 4~
electrode, separator and negative electrode (seven positive electrodes) are laminated were assembled. As two outer negative electrodes, one having a thickness of 175nm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, a lithium metallic foil (33 pm, 2.2 x 3.2 cm2, 1.6 x 2.2 cm2 for outer two foils) was attached to the negative electrode plate. The opposed area (7.04 cm2 x 6 + 3.52 cm2 x 2 =
49.28 cm2) of lithium metal was 50.0% of the area of the negative electrode (7.04 cm2 x 14 (both surfaces x 6, one surface x 2) = 98.56 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V
cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 680 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 400 mAh.
[Comparative Example 5]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 250 pm and a positive electrode having a thickness of 380 pm were obtained. Using the positive electrode (2.0 x 3.0 cm2), PAS negative electrode (2.2 x 3.2 cm2) and a polypropylene separator having a thickness of 25 um, two cells wherein the positive electrode, separator and negative electrode (seven negative electrodes) are laminated were assembled. As two outer positive electrodes, one having a thickness of 190 pm obtained by molding the slurry on one surface of an aluminum expanded metal having a thickness of 120 }zm in the same manner as in Example 4 was used. As the lithium metal, a lithium metallic foil (33 um, 2.0 x 3.0 cm2, 1.5 x 2.0 cm2 for outer two foils) was attached to the positive electrode plate. The opposed area (6 cm2 x 6 + 3 cm2 x 2 = 42 cm2 ) of lithium metal was 50.0% of the area of the positive electrode (6 cm2 x 14 (both surfaces x 6, one surface x 2) _ 84 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in the above respective Examples. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was a y 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours.
Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 550 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 320 mAh.
In Comparative Examples 4 and 5, although the thickness of lithium metal may be reduced to improve the charge and discharge characteristics, it is very complicated method, which is not suited for industrial production, to attach a lithium metallic foil having a thickness of about 30 um as a lower limit of the thickness for mass-production of lithium metallic foil on each one negative electrode, actually. That is, in order to reduce the thickness of the electrode so as to improve the charge and discharge characteristics, a further thin lithium metallic foil is required, whereby it becomes more difficult to conduct mass production and it becomes unsuitable for practical use.
As is apparent from the above respective Examples, the present invention can provide a method of carrying a lithium ion negative electrode or lithium ion positive electrode having a very large freedom considering the charge and discharge characteristics in a cell system having lithium ion originating in the negative electrode, namely cell system wherein lithium ion is previously carried on the negative electrode, or a cell system wherein lithium ion is previously carried on the positive electrode in addition to lithium ion contained intrinsically in the positive electrode.
[Example 7]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 180 um and a positive electrode having a thickness of 290 }.im were obtained. Using the positive electrode (5.4 cm in width x 37.0 cm in length), PAS negative electrode (5.6 cm in width x 39.0 cm in length) and polypropylene separator having a thickness of pm, two cells were assembled To contact-bond a lithium metallic foil, one surface of the negative electrode was 25 provided with a current collector portion (4.8 cm) capable of forming no active material of negative electrode (total length of the negative electrode is 3.9 cm + 4.8 cm). One obtained by contact-bonding the lithium metallic foil (160 pm, 5.6 x 4.8 cm2) on the current collector of negative 5 electrode was used and arranged to face the negative electrode and positive electrode, thereby to obtain a wound-type cylindrical cell (18650 type). The area (26.88 cm2) of lithium metal was 6.2% of the area of the negative electrode (436.8 cm2). The amount of lithium metal was about 250 mAh/g 10 based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples.
The total amount of lithium contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and 15 then decomposed. As a result, each of the above cells was charged at 4.2V for 12 hours at the maximum current of 500 mA. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, 20 and in the third discharge, the cell capacity was evaluated.
As a result, it was 2000 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1900 mAh. The energy density was calculated. As a result, 25 it was large such as 390 Wh/l.
[Example 8]
Using the same positive electrode, PAS negative electrode and separator as in Example 7, two cylindrical cells were assembled. As the current collector of positive electrode, a stainless steel (SUS316) expanded metal having a thickness of 240 -~im (porosity: 86%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) was used. To contact-bond a lithium metallic foil, one surface of the positive electrode was provided with a current collector portion (5.2 cm) capable of forming no active material of positive electrode (total length of the positive electrode is 37.0 cm + 5.2 cm). One obtained by contact-bonding the lithium metallic foil (150 pm, 5.4 x 5.2 cm2) on the current collector of positive electrode was used and arranged to face the negative electrode and positive electrode as shown in FIG. 8, thereby to obtain a wound-type cylindrical cell (18650 type). The area (28.08 cm2) of lithium metal was 7.0% of the area of the positive electrode (399.6 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
~
Each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V, and charged at a constant current of 500 mA until the cell voltage became 4.2 V, and then constant current/constant voltage charge of applying a constant voltage of 4.2 V was conducted for 12 hours. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 1980 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1850 mAh. The energy density was calculated. As a result, it was large such as 385 Wh/l.
[Comparative Example 6]
In the same manner as in Example 7, a PAS negative electrode having a thickness of 180 um and a positive electrode having a thickness of 290 um were obtained. Using the positive electrode (5.4 cm in width x 37.5 cm in length), PAS negative electrode (5.6 cm in width x 39.5 cm in length) and polypropylene separator having a thickness of pm, two cylindrical cells were assembled. Lithium metal was not arranged in the cell. The electrolytic solution was the same as in the above respective Examples. The total 25 amount of lithium ion contained in the cell was 1250 mAh/g based on the negative plate PAS.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 500 mA. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V.
This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 1500 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1450 mAh. The energy density was calculated. As a result, it was large such as 290 Wh/l.
As described above, when the amount of lithium ion originating in the negative electrode is 0 mAh/g or when lithium ion is not electrochemically carried in addition to lithium ion contained intrinsically in the positive electrode, a sufficient capacity could not be obtained.
[Example 9]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 200 um was obtained.
Then, 100 parts by weight of V205 (second type of the positive electrode) and 10 parts by weight of acetylene black were sufficiently mixed with a solution of 3.5 parts by weight of polyvinylidene fluoride powder in 80 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of an aluminum expanded metal having a thickness of 240 4m (porosity: 88%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 750 um. In addition, a slurry was molded on one surface of an aluminum expanded metal having a thickness of 120 um (porosity: 85%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 300 um.
Using the above positive electrode (2.0 x 3.0 cm2), PAS negative electrode (2.2 x 3.2 cm2) and a separator having a thickness of 25 pm, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 4 were assembled.
As two outer negative electrodes, one having a thickness of 300 pm obtained by molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 }im as described above was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (850 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2) of lithium metal was 5.6% of the area of the negative electrode (6 cm2 x 18 (both surfaces x 8, one surface x 2) = 108 cm2).
The amount of lithium metal was about 1000 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. One cell was allowed to stand at room temperature for seven days, and then decomposed. As a result, lithium metal completely disappeared. Each of the above cells was charged at 3.3 V
for 12hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 1.0 V. This 3.3 V-1.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 600 mAh.
Industrial Applicability As described above, the organic electrolytic cell according to the present invention is extremely useful because of its easy production, high capacity and high voltage, excellent charge and discharge characteristics, and high safety.
Disclosure of the Invention To attain these objects, the organic electrolytic cell of the present invention has the following construction.
That is, aspect 1 of the present invention provides an organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the negative electrode capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which a plurality of positive electrode plates, separators and negative electrode plates are laminated in sequence or a wound structure, wherein the lithium ion originating in the negative electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the negative electrode.
Aspect 2 of the present invention provides an organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the positive electrode and an active material of the negative electrode, each capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which a plurality of positive electrode plates, separators and negative electrode plates are laminated in sequence or a wound structure, wherein at least one portion of the lithium ion originating in the positive electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the positive electrode.
Brief Description of the Drawings FIG. 1 is a view illustrating the arrangement of a first embodiment of electrodes in the cell according to the present invention.
FIG. 2 is a view illustrating the arrangement of a second embodiment of electrodes in the cell according to the present invention.
FIG. 3 is a view illustrating the arrangement of a third embodiment of electrodes in the cell according to the present invention.
FIG. 4 is a view illustrating the arrangement of a fourth embodiment of electrodes in the cell according to the present invention.
FIG. 5 is a view illustrating the arrangement of a fifth embodiment of electrodes in the cell according to the present invention.
FIG. 6 is a view illustrating the arrangement of a sixth embodiment of electrodes in the cell according to the present invention.
FIG. 7 is a view illustrating the arrangement of a seventh embodiment of electrodes in the cell according to 7a the present invention.
FIG. 8 is a view illustrating the arrangement of an eighth embodiment of electrodes in the cell according to the present invention.
FIG. 9 is a view illustrating the arrangement of a ninth embodiment of electrodes in the cell according to the present invention.
Best Mode for Carrying Out the Invention The active material of the negative electrode in the organic electrolytic cell of the present invention may be any one capable of reversibly carrying lithium ion, and examples thereof include graphite, various carbon materials, polyacene substance, tin oxide, silicon oxide and the like.
Among them, it is preferred to use an infusible and insoluble substance having a polyacene skeletal structure and a -772?~4-4 $
hydrogen/carbon atomic ratio of 0.50 to 0.05, the substance being a heat-treated product of an aromatic condensation polymer, because a high capacity can be obtained.
The aromatic condensation polymer is a condensate of an aromatic hydrocarbon compound and aldehydes. As the aromatic hydrocarbon compound, for example, so-called phenols such as phenol, cresol, xylenol and the like can be suitably used. There can also be used methylenebisphenols represented by the following formula:
-CH CF-I 3) ~ 3}x 2 Y
wherein x and y are independently 0, 1 or 2, or hydroxybiphenyls or hydroxynaphthalenes. For practical purpose, phenols, particularly phenol, are preferred.
As the aromatic condensation polymer, there can also be used a modified aromatic condensation polymer wherein a portion of the aromatic hydrocarbon compound having phenolic hydroxyl groups is replaced with an aromatic hydrocarbon compound having no phenolic hydroxyl group such.
as xylene, toluene or aniline, for example,.a condensate of phenol,xylene and formaldehyde. Furthermore, there can also be used a modified aromatic polymer wherein the above portion is replaced with melamine or urea. A furan resin 772,14-4 is also preferred.
As the aldehyde, it is possible to use aldehydes such as formaldehyde, acetaldehyde and. furfural, but.
formaldehyde- is preferred. A pheno.lformaldehyde condensate- may be any of a novolak type, a resol type or a mixture thereof.
The infusible and insoluble substance can be obtained by a heat treatment of the above aromatic polymer, and includes all of infusible and insoluble substances having a polyacene skeletal structure described in Japanese'Patent Publication Nos. 44212/19S9 and 24024/1991.
The infusible and insoluble substance used in the present invention can. also be produced as follows . That is, an infusible and insoluble substance having a hydrogen/ca=bon atomic ratio (hereinafter referred to as:
H/C) of 0. 50 to 0. 05, pref erably 0. 35 to 0=.10 can be obtained by gradually heating the aromatic condensa=Cion polymer up to -a proper temperature of 400 to 800r, in 'a non-oxidizing atmosphere (including a vacuum).
It is also -possible to obtein an infusible and insoluble- substance having a specific surface area, measured by the. BET method, of not'less than 600 m2/g according to the method described in Japanese. Patent Publication No. 24024/1991. For example, an infusible and insoluble substance having the above H/C and having a specific surface area, rneasured by =the BET method, of not less than 600 m2/g can also be obtained by preparing a solution containing an initial condensate of an aromatic condensation polymer and an inorganic salt such as zinc chloride; heating the solution to cure it in a mold;
5 gradually heating the cured matter in a non-oxidizing atmosphere (including a vacuum) up to a temperature of 350 to 800 C, preferably up to a proper temperature of 400 to 750 C; and then sufficiently washing it with water, diluted hydrochloric acid or the like.
10 With respect to the infusible and insoluble substance used in the present invention, according to X-ray diffraction (CuKa), the main peak is observed at 2e=24 or less, and besides another peak is observed at between 28=41 and 2e=46 , in addition to the main peak. Namely, it is suggested that the infusible and insoluble substrate has a polyacene skeletal structure wherein an aromatic polycyclic structure is moderately developed, and takes an amorphous structure. Thus the substrate can be doped stably with lithium ion and, therefore, it is useful as an active material for cells.
It is preferred that this infusible and insoluble substance has H/C ranging from 0.50 to 0.05. When H/C
exceeds 0.50, the aromatic polycyclic structure does not sufficiently develop, and thus it is impossible to conduct doping and undoping of lithium ion smoothly, and when a cell is assembled, charge and discharge efficiency is lowered.
On the other hand, when H/C is less than 0.05, the capacity "of the cell of the present invention is likely to be lowered.
The negative electrode in the organic electrolytic cell according to the present invention is cam:posed of the above infusible and insoluble substance (herein'after referred to as P+AS), and practically, it is preferred.to use a form obtained by forming PAS in an easily formable form such as a powdery form, a granular form or a short fiber form with a binder. As the binder, there can be used fluorine-containing resins such, as polyethylene tetrafluoride and polyvinylidene fluoride, and thermoplastic resins such as polypropylene and polyethylene.
It is preferred to use a fluorine binder. Use of a fluorine binder having a fluorine/carbon atomic ratio (herei.nafter referred to as F/C) of less than 1.5 and not less than 0'. 75 is preferred, and use of a-fluorine binder havi.ng a fluorine/carbon atomic ratio of less than 1.3 and not less than 0.75 is more preferred.
The fluorine binder includes, for example, 20. polyvinylidene fluoride, vinylidene fluoride-ethylene trifluoride copolymer,, ethylene-ethylene tetrafluoride copolymer, propylene-ethylene tetrafluoride or the like.
Furthermore, it is also possible to use a fluorine-containing polymer wherein hydrogens at the principal chain are replaced with alkyl groups. In the case of the polyvinylidene fluoride, F/C is 1. In the case of.the vinylidene fluoride-ethylene trifluoride copolymer, when the molar fractions of vinylidene fluoride are 50% and 80%, F/C values become 1.25 and 1.10, respectively. In the case of the propylene-ethylene tetrafluoride copolymer, when the molar fraction of propylene is 50%, F/C becomes 0.75.
Among them, polyvinylidene fluoride, and a vinylidene fluoride-ethylene trifluoride copolymer wherein the molar fraction of vinylidene fluoride is not less than 50% are preferred. For practical purpose, polyvinylidene fluoride is preferred.
When using these binders, it is possible to sufficiently utilize the doping ability (capacity) with lithium ion which PAS has.
When using PAS, oxide or the like as the active material of negative electrode, if necessary, electrically conductive materials such as acetylene black, graphite, metallic powder and the like may be appropriately added in the negative electrode of the organic electrolytic cell of the present invention.
The active material of positive electrode in the organic electrolytic cell according to aspect 1 of the present invention is not specifically limited, for example there can be used lithium-containing metallic oxides capable of electrochemically doping with lithium ion and electrochemically undoping lithium ion, which can be represented by the general formula LixMyOz (M is a metal, or can be two or more metals) such as LixCo02, LixNi02, LixMn02 or LixFe02r or oxides of transition metals such as cobalt, manganese and nickel. The above electrically conductive polymers such as PAS can also be suitably used.
Particularly, when a high voltage and high capacity are required, a lithium-containing oxide having a voltage of not less than 4 V vs lithium metal is preferred. Among them, lithium-containing cobalt oxides, lithium-containing nickel oxides or lithium-containing cobalt-nickel double oxides are particularly preferred.
The active material of positive electrode in the organic electrolytic cell according to aspect 2 of the present invention is not specifically limited, for example there can be used lithium-containing metallic oxides capable of reversibly carrying lithium ion, which can be represented by the general formula LixMyOz (wherein M is a metal, or can be two or more metals and x, y and z are each a positive number) such as LixCo02, LixNi02, LixMn02 or LixFe02r or oxides and sulfides of transition metals such as cobalt, manganese, vanadium, titanium and nickel. The above electrically conductive polymers such as PAS can be suitably used. These active materials of positive electrode can be roughly classified into two kinds. That is, they are an active material of positive electrode (referred to as a first type of an active material of positive electrode in the present invention) capable of emitting lithium ion through electrochemical oxidation, namely charge, 7721,4-4 such as lithium-containing cobalt oxides, litYaium-containing nickel oxides and lithium-containing cobalt-nickel double oxides, and the other active material of.
positive electrode (referred to as a second type of an active material of positive electrode in the present inven tion) .
Particularly, when a high voltage is required, a lithium-containing oxide having a voltage of 'not: less than 4 V vs lithium metal is preferred. Among them, lithium-containing cobalt oxides, lithium-containing=nickel oxides or lithium-containing cobalt-nickel double oxides are particularly preferred.
The positive electrode in the organic electrolytic cell of the present invention is one made by optionally adding;an electrically conductive material and a binder to the above active material and molding the mixture, and the kind and composition of the electrically conductive material and binder can be, appropri.ately specified.
As the electrically conductive material, a powder of a metal such as metallic nickel can be used. Carbon material such as active carbon, carbon black, acetylene black and graphite can be suitably used. A mixing ratio of these electrically conductive materials varies depending on the "electric conductivity of the active material, shape of the electrode, etc. , but it is suitable to add it in an amount of 2 to 40* based on the active material. .
The binder may be any one which is insoluble in-an electrolytic solution described hereinafter used in the organic electrolytic solution of the present invention.
There can be preferably used, for example, rubber binders such as SBR, fluorine-containing resins such as polyethylene tetrafluoride and polyvinylidene fluoride, and thermoplastic resins such as polypropylene and polyethylene. The mixing ratio is preferably not more than 20% based on the above active material.
As the solvent constituting the electrolytic solution used in the organic electrolytic solution of the present invention, an aprotic organic solvent is used. The aprotic organic solvent includes, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, 7 -butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane or the like. Furthermore, a mixed solution of two or more of these aprotic organic solvents can also be used.
Furthermore, as an electrolyte to be dissolved in the single or mixed solvent, any of electrolyte capable of forming lithium ions can be used. The electrolyte includes, for example, LiI, LiClO4 , LiAsFb , LiBF4 , LiPFb or the like.
The electrolyte and solvent are mixed in a state of being sufficiently dehydrated to give an electrolytic solution. To make the internal resistance by the electrolytic solution small, it is preferred to make the concentration of the electrolyte in the electrolytic solution at least 0.1 mol/1 and it is more preferred to make it 0.2 to 1.5 mol/l.
The current collector of positive electrode and current collector of negative electrode in the organic electrolytic cell of the present invention are each provided with pores piercing from a front surface to a back surface, and are made of materials such as expanded metal, punched metal, net, foamed material or the like. The form and number of these through pores are not specifically limited and can be appropriately determined so that lithium ions in the electrolytic solution described hereinafter can transfer between the front and back surfaces of the electrode without being interrupted by the current collectors of electrodes.
For example, when the proportion (form and number) of the through pores is determined by the porosity of the electrode-current collector, it is preferred to make the porosity 10% or more, particularly 30% or more. The porosity of the electrode current collector is obtained by reducing a ratio of {1 - (weight of current collector/true specific gravity of current collector)/(apparent volume of current collector)} to percentage. When this porosity is small, the time of carrying lithium ion originating in the negative or positive electrode becomes long. On the other hand, when it is too large, the resulting cell has a high internal resistance and, therefore, the porosity is preferably determined by considering the desired cell characteristics, thickness of the electrode, safety, and kind of the current collector. As the material of the electrode-current collector, there can be used various materials which are generally proposed in lithium cells.
Aluminum and stainless steel can be used as the current collector of positive electrode, whereas, stainless steel, copper and nickel can be used as the current collector of negative electrode. With respect to the current collector of positive electrode of the organic electrolytic cell according to aspect 2, when lithium metal is directly attached as described hereinafter, it is preferred to use a material, which does not make an alloy with lithium metal and has resistance to electrochemical oxidation, such as stainless steel.
In the organic electrolytic cell according to aspect 1 of the present invention, lithium ion originating in the negative electrode is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode and the opposed area of the lithium metal is not more than 40%, preferably not more than 30% of the area of the negative electrode. In the organic electrolytic cell according to aspect 2 of the present invention, lithium ion originating in the positive electrode is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode and the opposed area of the lithium metal is not more than 40%, preferably not more than 30% of the area of the positive electrode. The term "lithium metal" used in this specification refer to any material, which contains at least lithium and is capable of supplying lithium ions, such as lithium metal, lithium-aluminum alloy or the like.
In the case of a metallic lithium foil or metallic lithium plate, the opposed area of lithium metal is an area at the portion where the foil or plate and the negative or positive electrode are faced each other. That is, in the case of those having the form shown in FIG. 1, FIG. 2, FIG. 4 and FIG. 5 to be described hereinafter as embodiments of the present invention, it is an area of one surface. In the case of those having the form shown in FIG. 3 and FIG. 6, it is the total of areas of both surfaces. In the case of lithium metal formed in a cylindrical or prismatic shape, it is an area of the side. Any of the area of negative electrode and area of positive electrode is an area at the portion where the negative electrode and positive electrode are faced each other.
When a lithium metallic foil is attached on both surfaces of a negative electrode plate molded on both surfaces of a copper foil, the opposed area of lithium metal becomes 100% of the area of negative electrode. When a lithium metallic foil is attached on one surface of a negative electrode plate molded into an expanded metal, the opposed area of lithium metal becomes 50% of the area of negative electrode.
When a lithium metallic foil is attached on both surfaces of a positive electrode plate molded on both surfaces of an aluminum foil, the opposed area of lithium metal becomes 100% of the area of positive electrode. When a lithium metallic foil is attached on one surface of a positive electrode plate molded into an expanded metal, the opposed area of lithium metal becomes 50% of the area of positive electrode.
In the organic electrolytic cell according to the present invention, by locally arranging lithium ion originating in the negative or positive electrode at a specific position, the opposed area of lithium metal is made 40% or less, preferably 30% or less of the area of negative electrode or area of positive electrode, thereby making it possible to improve the freedom of the cell design and mass-productivity and to afford excellent charge and discharge characteristics. That is, it is very complicated to attach a lithium metal on almost all of the negative or positive electrode, like the above example, and it is not suited for industrial production and it becomes difficult to conduct mass-production. When the opposed area of lithium metal exceeds 40% of the area of negative electrode or area of positive electrode, the thickness of the electrode is decided by that of lithium metal, thereby to cause a problem that desired charge and discharge characteristics can not be obtained.
In the organic electrolytic cell according to aspect 1 of the present invention, the total amount of lithium ion contained the cell is preferably not less than 500 mAh/g and the amount of lithium ion originating in the negative electrode is preferably not less than 100 mAh/g, based on the active material of negative electrode. The total amount of lithium ion contained the cell is the total of the amount of lithium ion originating in the positive electrode, that of lithium ion originating in the electrolytic solution and that of lithium ion originating in 5 the negative electrode. Lithium ion originating in the positive electrode is lithium ion contained in the positive electrode on assembly of the cell, and a portion or all of the lithium ion is supplied to the negative electrode through an operation of applying a current from an external 10 circuit (charge).
In the organic electrolytic cell according to aspect 2 of the present invention, lithium ion originating in the positive electrode is lithium ion contained in the positive electrode and at least one portion, namely a 15 portion or all of lithium ion is carried by electrochemical contact with lithium metal arranged to face the negative or positive electrode. For example, when using LiCo02 as the active material of positive electrode, LiCoO2 has already contained lithium ion on assembly of the cell, but lithium 20 ion originating in the positive electrode is obtained by further adding lithium ion carried through electrochemical contact with lithium metal. On the other hand, when using V205 as the active material of positive electrode, since this material does not contain lithium ion, all of lithium ion originating in the positive electrode is carried by electrochemical contact with lithium metal. At least one portion, namely portion or all of this lithium ion originating in the positive electrode is supplied to the negative electrode through an operation of applying a current from an external circuit (charge). Then, the electrochemical contact between lithium metal and the positive electrode initiates when the electrolytic solution is poured into the cell system. When using the above first type of an active material of positive electrode, since said active material of positive electrode has already contained releasable lithium ion, it becomes possible to charge the cell system immediately after pouring the electrolytic solution into the cell system. Also when using the second type of an active material of positive electrode, it is possible to charge the cell system before all lithium ion is completely charged on the active material of positive electrode after pouring the electrolytic solution into the cell system. The above charge operation is effective to reduce the carrying time and to prevent the positive electrode from being in an over-discharge state, thereby preventing deterioration of the positive electrode due to the carrying operation of lithium ion.
Lithium ion originating in the electrolytic solution in the organic electrolytic cell of the present invention is lithium ion in the electrolytic solution contained in the separator, positive electrode and negative electrode, whereas, lithium ion originating in the negative electrode is lithium ion carried on the active material of negative electrode and is lithium ion other than lithium ion originating in the positive electrode and lithium ion originating in electrolytic solution.
FIG. 1 to FIG. 6 each illustrate an embodiment of a cell of the type wherein plural pairs of positive electrode plates, a separator and a negative electrode plate are laminated in sequence in the organic electrolytic cell of the present invention.
FIG. 1 illustrates one embodiment of the arrangement of electrodes in a casing of the cell of the above type. In this embodiment, a negative electrode 2 molded on both surfaces of a current collector 2' of negative electrode and a lithium metal 4 contact-bonded on a lithium metal current collector 4' made of a stainless mesh or a copper expanded metal, which is arranged at the lower portion of a multi-layer unit, are connected through a conductor 5. A positive electrode 1 molded on both surfaces of a current collector 1' of positive electrode is laminated via the above negative electrode 2 and separator 3, and is connected through a conductor 5'. The above current collector 2' of negative electrode and lithium metal current collector 4' can also be welded directly.
FIG. 2 illustrates a modified embodiment of the arrangement of electrodes shown in FIG. 1. In this cell, the lithium metal 4 contact-bonded on the lithium metal current collector 4' is arranged at the upper and lower portions of the multi-layer unit, respectively.
Another modified embodiment shown in FIG. 3 illustrates that the lithium metal 4 is arranged in the center of the multi-layer unit.
FIG. 4 illustrates another embodiment _of the arrangement of. electrodes of the above type. In this embodiment, the positive electrode 1 molded on both surfaces of the current collector 1' of positive electrode and the lithium metal 4 contact-bonded on the lithium metal current collector 4' made of a stainless mesh or a copper expanded metal, which is arranged at the lower portion of the multi - layer unit, are connected through the conductor 5'.
The negative electrode 2 molded.on both surfaces of the current collector 2' of negative electrode is laminated via .
the above positive electrode 1 and separator 3, and is connected through the conductor 5. The above current collector 1' of positive electrode and lithium metal current collector 4' can also be welded directly:
FIG. 5 illustrates a modified einbodiment of the arrangement of electrodes shown in FIG. 4. In this cell, the lithium metal 4 contact-bonded on the lithium metal current collector 4' is arranged at the upper and lower portions of the multi-layer unit, respectively.
Another modified embodiment shown in FIG. 6 illustrates that the lithium metal 4 is.arranged in the center of the multi-layer unit.
In the -above respective embodiments, the .'current collector 1` of positive electrode and current collector 2' of negative electrode are each provided with pores (not shown) piercing from the front surface to the back surface, and a terminal of positive: electrode and a 1p terminal of negative electrode of the cell are connected with them,.respectively.
In the embodiments.shown in .FIG. 1 to FIG. 3, the current collector 1' of positive electrode can be directly welded without providing the conductor 5. In the embodiments shown in FIG. 4 to FIG. 6, the current collector 2' of negative electrode can be directly welded without providing the .conductor 5.
As mentioned above, in the arrangement of the.
electrodes of a multi-layer type cell, the position of the 20 lithium metal 4 to be arranged can be appropri.ately changed as shown in the above embodiments.
FIG. 7 to FIG. 9 each illustrate an embodiment of the arrangement of electrodes of a cell having a wound-type structure used in a cylindrical cell as the embodiment of the_present invention. In the arrangement of these cells; a positive.electrode 1 and a negative electrode .2 are molded on a current collector (in the drawing, the current collector is eliminated). FIG. 7 illustrates an embod.iment wherein the lithium metal 4 is attached on the current collector of an outer-most negative electrode 2 (in the drawing, only the lithium metal 4 is shown at the' portion where the lithium metal is lami.nated) , whereas, FIG. 8 illustrates an embodiment wherein the-lithium metal 4 is attached on the current collector of an outer-most positive electrode .1 ( i.n the drawing; only the -lq lithium metal 4 is shown. at the portion where the lithium metal is laminated)-.. FIG. 9 illustrates an embodiment wherein the lithium metal 4 having a columnar.shape is arranged in the center of a wound-type structure.
In the above arrangement-of the electrodes; -the separator 3 is made of a porous material, which is durable against the electrolytic solution or the electrode active material and which has open pores and is electrically non-conductive. There can be usually used a cloth., non-woven fabric or porous material made of glass fiber, 20 polyethylene or polypropylene. To decrease the internal resistance of the cell; the separator 3 is preferably as thin as possible. Its thickness, however, is determined by appropriately considering the amount of electrolytic solution held, permeability, strength or the like. The separator 3 is impregnated with the electrolytic solution, and in the electrolytic solution, the above compound capable of forming lithium ions with which doping is made is dissolved in an aprotic organic solvent. The electrolytic solution is usually a liquid and impregnated into the separator 3, but it can also be used, without any separator 3, after being made into gel or a solid for preventing leakage of the solution.
In the above embodiments, the negative or positive electrode is made contact with lithium metal (lithium metal in these embodiments) via the conductor 5 or 5' made of nickel, copper or stainless steel, or attaching lithium metal on the current collector of negative electrode or the current collector of positive electrode, but the organic electrolytic cell of the present invention is not specifically limited to this structure. For example, lithium metal may also be made contact by directly attaching it on the negative or positive electrode, or by directly attaching it on a negative electrode case or a positive electrode case. That is, it is necessary to arrange so that, when the electrolytic solution is poured on assembly of the cell, any of the negative or positive electrode is electrochemically made contact with lithium metal thereby to carry lithium ion on an active material of negative electrode or an active material of positive electrode and the active material of negative electrode via the electrolytic solution.
Particularly, by filling the pore portion of an electrically conductive porous material such as stainless steel mesh as the lithium metal current collector with 80%
or more of lithium metal, a space is hardly formed between electrodes by disappearance of lithium metal even if lithium ion is doped. Thus, lithium ion is smoothly carried on the active material of negative electrode or the active material of positive electrode.
To the contrary, there can also be employed a method of arranging lithium metal in a transverse direction of the negative electrode plate or positive electrode plate and carrying lithium ion on the active material of negative electrode or active material of positive electrode by electrochemical contact between the negative or positive electrode and lithium metal in the cell. However, according to this method, it is impossible to avoid a problem that unevenness in doping in the cell increases and lithium metal is partially deposited on the negative electrode, resulting in long carrying time. Accordingly, in the present invention, it is required to arrange so that the positive or negative electrode and lithium metal face each other.
In this cell, the amount of lithium ion originating in the negative electrode or lithium ion originating in the positive electrode can be appropriately determined by the desired cell, active material of negative electrode or active material of positive electrode, but a particularly high-capacity cell can be obtained by using PAS
a M
as the active material of negative electrode and satisfying the following conditions. That is, when using PAS as the active material of negative electrode, the total amount of lithium ion in the cell is preferably not less than 500 mAh/g, more preferably not less than 600 mAh/g, based on PAS of negative electrode so as to obtain a sufficient capacity.
In the organic electrolytic cell according to aspect 1, the amount of lithium ion originating in the negative electrode is preferably not less than 100 mAh/g, more preferably not less than 150 mAh/g, based on PAS of negative electrode. When the amount of lithium ion originating in the negative electrode is less than 100 mAh/g even if the total amount of lithium ion is not less than 500 mAh/g based on PAS of negative electrode, there is some possibility of causing a problem that a sufficient capacity can not be obtained. When using a lithium-containing metal oxide as the positive electrode, a high capacity can be obtained by adjusting the amount of lithium ion originating in the negative electrode to 600 mAh/g or less based on PAS of negative electrode, which is preferred. Although the amount of lithium ion originating in the positive electrode and that of lithium ion originating in the electrolytic solution can be appropriately determined, the amount of lithium ion originating in the positive electrode is preferably not less than 300 mAh/g based on PAS of negative electrode so as to obtain a high capacity when using a lithium-containing metal oxide as the positive electrode.
In the organic electrolytic cell according to aspect 2, when using the above first type of an active material of positive electrode, lithium ion originating in the positive electrode is preferably carried in the amount of not less than 100 mAh/g, more preferably not less than 150 mAh/g, based on PAS of negative electrode, in addition to lithium ion contained intrinsically in the positive electrode so as to obtain a high capability. In this organic electrolytic cell, lithium ion originating in the negative electrode may be previously carried on PAS as the active material of negative electrode. Particularly, when using the above second type of an active material of positive electrode, since the amount of lithium ion to be carried increases, it is effective to separately carry a required amount of lithium ion on the negative or positive electrode so as to reduce the carrying time.
The shape of the organic electrolytic cell according to the present invention includes, for example, cylindrical shape, rectangular shape and box shape, but is not specifically limited.
[Example 1]
A phenol-formaldehyde resin having a thickness of 0.5 mm was put in a silicon carbide heating element, and heat-treated by heating to 500 C under a nitrogen atmosphere at a rate of 50 C/hour and then heating to 650 C at a rate of 10- C/hour, thereby to synthesize PAS. The PAS plate thus obtained was ground by using a disc mill to obtain PAS powder having an average particle diameter of about 7Am. The H/C
ratio of this PAS powder was 0.22.
Then, 100 parts by weight of the PAS powder and 10 parts by weight of acetylene black were sufficiently mixed with a solution of 10 parts by weight of polyvinylidene fluoride powder in 120 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of a copper expanded metal having a thickness of 60 ,u m (porosity: 70%) (manufactured by Sank Co., LW: 1 mm, SW:
0. 5 mm) to obtain a PAS negative electrode having a thickness of 520 gm. In addition, 100 parts by weight of LiCoO2 (first type of positive electrode) and 5 parts by weight of graphite were sufficiently mixed with a solution of 3.5 parts by weight of polyvinylidene fluoride powder in 50 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of an aluminum expanded metal having a thickness of 240 9 m (porosity: 88%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 780 gm.
Using the above positive electrode (2.0 X 3.0 cm2), PAS negative electrode (2. 2 X 3. 2 cmz ) and a polypropylene separator having a thickness of 25 am, two cells wherein the positive electrode, separator and negative electrode (four positive electrodes) are laminated shown in FIG. 1 were assembled. As two outer negative electrodes, one having a thickness of 290 pm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (240 pm, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 3) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding.
The opposed area (7.04 cm2) of lithium metal was 12.5% of the area of the negative electrode (7.04 cm2 x 8 (both surfaces x 3, one surface x 2) = 56.32 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. As the electrolytic solution, a solution of LiPF6 at a concentration of 1 mol/l in a 1:1 (volume ratio) mixed solution of ethylene carbonate and diethyl carbonate was used. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 720 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated.
As a result, it was 300 mAh.
[Example 2]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 182 um and a positive electrode having a thickness of 271 um were obtained. Using the positive electrode (2.0 x 3.0 cmz), PAS negative electrode (2.2 x 3.2 cm2) and a polypropylene separator having a thickness of 25 1um, two cells wherein the positive electrode, separator and negative electrode (nine positive electrodes) are laminated shown in FIG. 1 were assembled.
As two outer negative electrodes, one having a thickness of 130 pm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (289 um, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (7.04 cm2) of lithium metal was 5.6% of the area of the negative electrode (7.04 cm2 x 18 (both surfaces x 8, one surface x 2) = 126.72 cm2) . The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA
until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Example 3]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine positive electrodes) are laminated shown in FIG. 1 were assembled. As two outer negative electrodes, one having a thickness of 130 Um obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (100 um, 2.2 x 3.2 cm2) on a stainless steel net having a thickness of 80 pm was used and two plates were arranged at the upper and lower portions of an electrode multi-layer unit so as to face the negative electrode. The negative electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (7.04 cm2 x 2 (both surfaces x 2) = 14.08 cm2) of lithium metal was 11.1%
of the area of the negative electrode (7.04 cm2 x 18 (both surfaces x 8, one surface x 2) = 126.72 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS.
One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated.
As a result, it was 620 mAh.
[Example 4]
The slurry obtained in Example 1 was molded on one 5 surface of an aluminum expanded metal having a thickness of 120 pm (porosity: 85%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 400 pm.
Using the same positive electrode, PAS negative 10 electrode and separator as in Example 1, two cells wherein the positive electrode, separator and negative electrode (four negative electrodes) are laminated shown in FIG. 4 were assembled. As two outer positive electrodes, a positive electrode having a thickness of 400 pm obtained by 15 molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 pm as described above was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (280 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 pm was used 20 and was arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 3) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2) of lithium metal 25 was 12.5% of the area of the positive electrode (6 cm2 x 8 (both surfaces x 3, one surface x 2) = 48 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V
cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 720 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 300 mAh.
[Example 5]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 4 were assembled. As two outer positive electrodes, a positive electrode having a thickness of 150 um obtained by molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 pm in the same manner as in Example 4 was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (230 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 lim was used and arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cmz) of lithium metal was 5.6% of the area of the positive electrode (6 cmZ x 18 (both surfaces x 8, one surface x 2) = 108 cm`). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 4. Also, the electrolytic solution was the same as in the above repective Examples.
The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours.
Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Example 6]
Using the same positive electrode, PAS negative electrode and separator as in Example 2, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 5 were assembled. Two outer positive electrodes were the same as in Example 5. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (120 pm, 2.0 x 3.0 cm 2) on a stainless steel net having a thickness of 80 pm was used and arranged to face the positive electrode.
The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2 x 2 (both surfaces x 2) = 12 cm2) of lithium metal was 11.1% of the area of the positive electrode (6 cm2 X 18 (both surfaces x 8, one surface x 2) = 108 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 4. Also, the electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. Then, one cell was allowed to stand at room temperature for two days and decomposed.
As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 650 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 620 mAh.
[Comparative Example 11 In the same manner as in Examples 1 and 4, except that an aluminum foil having a thickness of 30 pm was used as the current collector of the positive electrode and a copper foil having a thickness of 18 um was used as the current collector of the negative electrode, two kinds of cells were assembled. Each of the. celis was allowed to stand at room .temperature for 20 days, and then decomposed. As a result, almost all of lithium metal remained in both of the cells.
[Comparative Example 2]
In the sa,me manner as in Examples 1 and 4,. except that an aluminum foil having a thickness of 30 ,etm was used as the current collector of the positive electrode-, two kinds of cells were assembled. Each of the cells was allowed to stand at room temperature for 20 days, and then decomposed.
10 As a result, almost.all.of lithium metal remained in both of the cells.
[Comparative Example 3]
In the same manner as in Examples i and 4, except that a copper foil having a thickness of 18 l.Lm was used as the current collector of the negative electrode, two kinds of cells were assembled. Each of 'the cells was allowed to stand at room temperature for=20 days, and then decomposed. As a result, almost all of lithium metal remained in .both.
of the cells.
20 [Comparative Example 4]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 290 9 m and a positive electrode having a thickness of 438 9 mwere obtained. Using the positive electrode (2.0 X 3.0 cm2), PAS negative electrode (2.2 X 3.2 cm2) and polypropylene separator having a thickness of 25 gm, two cells wherein the positive 4~
electrode, separator and negative electrode (seven positive electrodes) are laminated were assembled. As two outer negative electrodes, one having a thickness of 175nm obtained by peeling off one of the above negative electrodes molded on both surfaces was used. As the lithium metal, a lithium metallic foil (33 pm, 2.2 x 3.2 cm2, 1.6 x 2.2 cm2 for outer two foils) was attached to the negative electrode plate. The opposed area (7.04 cm2 x 6 + 3.52 cm2 x 2 =
49.28 cm2) of lithium metal was 50.0% of the area of the negative electrode (7.04 cm2 x 14 (both surfaces x 6, one surface x 2) = 98.56 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in Example 1. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V
cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 680 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 400 mAh.
[Comparative Example 5]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 250 pm and a positive electrode having a thickness of 380 pm were obtained. Using the positive electrode (2.0 x 3.0 cm2), PAS negative electrode (2.2 x 3.2 cm2) and a polypropylene separator having a thickness of 25 um, two cells wherein the positive electrode, separator and negative electrode (seven negative electrodes) are laminated were assembled. As two outer positive electrodes, one having a thickness of 190 pm obtained by molding the slurry on one surface of an aluminum expanded metal having a thickness of 120 }zm in the same manner as in Example 4 was used. As the lithium metal, a lithium metallic foil (33 um, 2.0 x 3.0 cm2, 1.5 x 2.0 cm2 for outer two foils) was attached to the positive electrode plate. The opposed area (6 cm2 x 6 + 3 cm2 x 2 = 42 cm2 ) of lithium metal was 50.0% of the area of the positive electrode (6 cm2 x 14 (both surfaces x 6, one surface x 2) _ 84 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The total thickness of the electrode, separator and lithium metal was almost the same as in the above respective Examples. Also, the electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was a y 1500 mAh/g based on the negative plate PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours.
Then, one cell was allowed to stand at room temperature for two days and decomposed. As a result, lithium metal completely disappeared.
Each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V, and charged at 4.2V for 12 hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 550 mAh. In the fourth cycle, discharge at constant current of 350 mA was conducted and the cell capacity was evaluated. As a result, it was 320 mAh.
In Comparative Examples 4 and 5, although the thickness of lithium metal may be reduced to improve the charge and discharge characteristics, it is very complicated method, which is not suited for industrial production, to attach a lithium metallic foil having a thickness of about 30 um as a lower limit of the thickness for mass-production of lithium metallic foil on each one negative electrode, actually. That is, in order to reduce the thickness of the electrode so as to improve the charge and discharge characteristics, a further thin lithium metallic foil is required, whereby it becomes more difficult to conduct mass production and it becomes unsuitable for practical use.
As is apparent from the above respective Examples, the present invention can provide a method of carrying a lithium ion negative electrode or lithium ion positive electrode having a very large freedom considering the charge and discharge characteristics in a cell system having lithium ion originating in the negative electrode, namely cell system wherein lithium ion is previously carried on the negative electrode, or a cell system wherein lithium ion is previously carried on the positive electrode in addition to lithium ion contained intrinsically in the positive electrode.
[Example 7]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 180 um and a positive electrode having a thickness of 290 }.im were obtained. Using the positive electrode (5.4 cm in width x 37.0 cm in length), PAS negative electrode (5.6 cm in width x 39.0 cm in length) and polypropylene separator having a thickness of pm, two cells were assembled To contact-bond a lithium metallic foil, one surface of the negative electrode was 25 provided with a current collector portion (4.8 cm) capable of forming no active material of negative electrode (total length of the negative electrode is 3.9 cm + 4.8 cm). One obtained by contact-bonding the lithium metallic foil (160 pm, 5.6 x 4.8 cm2) on the current collector of negative 5 electrode was used and arranged to face the negative electrode and positive electrode, thereby to obtain a wound-type cylindrical cell (18650 type). The area (26.88 cm2) of lithium metal was 6.2% of the area of the negative electrode (436.8 cm2). The amount of lithium metal was about 250 mAh/g 10 based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples.
The total amount of lithium contained in the cell was 1500 mAh/g based on the negative electrode PAS. One cell was allowed to stand at room temperature for two days, and 15 then decomposed. As a result, each of the above cells was charged at 4.2V for 12 hours at the maximum current of 500 mA. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, 20 and in the third discharge, the cell capacity was evaluated.
As a result, it was 2000 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1900 mAh. The energy density was calculated. As a result, 25 it was large such as 390 Wh/l.
[Example 8]
Using the same positive electrode, PAS negative electrode and separator as in Example 7, two cylindrical cells were assembled. As the current collector of positive electrode, a stainless steel (SUS316) expanded metal having a thickness of 240 -~im (porosity: 86%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) was used. To contact-bond a lithium metallic foil, one surface of the positive electrode was provided with a current collector portion (5.2 cm) capable of forming no active material of positive electrode (total length of the positive electrode is 37.0 cm + 5.2 cm). One obtained by contact-bonding the lithium metallic foil (150 pm, 5.4 x 5.2 cm2) on the current collector of positive electrode was used and arranged to face the negative electrode and positive electrode as shown in FIG. 8, thereby to obtain a wound-type cylindrical cell (18650 type). The area (28.08 cm2) of lithium metal was 7.0% of the area of the positive electrode (399.6 cm2). The amount of lithium metal was about 250 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in the above respective Examples. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative electrode PAS. Immediately after pouring the electrolytic solution, each of the cells was charged at a constant current of 150 mA for 4 hours. One cell was allowed to stand at room temperature for two days, and then decomposed. As a result, lithium metal completely disappeared.
~
Each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V, and charged at a constant current of 500 mA until the cell voltage became 4.2 V, and then constant current/constant voltage charge of applying a constant voltage of 4.2 V was conducted for 12 hours. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V. This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 1980 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1850 mAh. The energy density was calculated. As a result, it was large such as 385 Wh/l.
[Comparative Example 6]
In the same manner as in Example 7, a PAS negative electrode having a thickness of 180 um and a positive electrode having a thickness of 290 um were obtained. Using the positive electrode (5.4 cm in width x 37.5 cm in length), PAS negative electrode (5.6 cm in width x 39.5 cm in length) and polypropylene separator having a thickness of pm, two cylindrical cells were assembled. Lithium metal was not arranged in the cell. The electrolytic solution was the same as in the above respective Examples. The total 25 amount of lithium ion contained in the cell was 1250 mAh/g based on the negative plate PAS.
Each of the above cells was charged at 4.2V for 12 hours at the maximum current of 500 mA. Subsequently, each of the above cells was discharged at a constant current of 200 mA until the cell voltage became 2.0 V.
This 4.2 V-2.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 1500 mAh. In the fourth cycle, discharge at constant current of 1000 mA was conducted and the cell capacity was evaluated. As a result, it was 1450 mAh. The energy density was calculated. As a result, it was large such as 290 Wh/l.
As described above, when the amount of lithium ion originating in the negative electrode is 0 mAh/g or when lithium ion is not electrochemically carried in addition to lithium ion contained intrinsically in the positive electrode, a sufficient capacity could not be obtained.
[Example 9]
In the same manner as in Example 1, a PAS negative electrode having a thickness of 200 um was obtained.
Then, 100 parts by weight of V205 (second type of the positive electrode) and 10 parts by weight of acetylene black were sufficiently mixed with a solution of 3.5 parts by weight of polyvinylidene fluoride powder in 80 parts by weight of N-methyl pyrrolidone to obtain a slurry. The slurry was molded on both surfaces of an aluminum expanded metal having a thickness of 240 4m (porosity: 88%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 750 um. In addition, a slurry was molded on one surface of an aluminum expanded metal having a thickness of 120 um (porosity: 85%) (manufactured by Sank Co., LW: 2 mm, SW: 1 mm) to obtain a positive electrode having a thickness of 300 um.
Using the above positive electrode (2.0 x 3.0 cm2), PAS negative electrode (2.2 x 3.2 cm2) and a separator having a thickness of 25 pm, two cells wherein the positive electrode, separator and negative electrode (nine negative electrodes) are laminated shown in FIG. 4 were assembled.
As two outer negative electrodes, one having a thickness of 300 pm obtained by molding the slurry on one surface of the aluminum expanded metal having a thickness of 120 }im as described above was used. As the lithium metal, one obtained by contact-bonding a lithium metallic foil (850 pm, 2.0 x 3.0 cm2) on a stainless steel net having a thickness of 80 um was used and was arranged to face the positive electrode. The positive electrodes (one surface x 2, both surfaces x 8) were respectively made contact with the stainless steel net, on which lithium metal was contact-bonded, through welding. The opposed area (6 cm2) of lithium metal was 5.6% of the area of the negative electrode (6 cm2 x 18 (both surfaces x 8, one surface x 2) = 108 cm2).
The amount of lithium metal was about 1000 mAh/g based on the negative electrode PAS. The electrolytic solution was the same as in Example 1. The total amount of lithium ion contained in the cell was 1500 mAh/g based on the negative plate PAS. One cell was allowed to stand at room temperature for seven days, and then decomposed. As a result, lithium metal completely disappeared. Each of the above cells was charged at 3.3 V
for 12hours at the maximum current of 150 mA. Subsequently, each of the above cells was discharged at a constant current of 70 mA until the cell voltage became 1.0 V. This 3.3 V-1.0 V cycle was repeated, and in the third discharge, the cell capacity was evaluated. As a result, it was 600 mAh.
Industrial Applicability As described above, the organic electrolytic cell according to the present invention is extremely useful because of its easy production, high capacity and high voltage, excellent charge and discharge characteristics, and high safety.
Claims (13)
1. An organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the negative electrode capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which the positive electrode has a plurality of positive electrode plates, the negative electrode has a plurality of negative electrode plates, and the positive electrode plates, separators and the negative electrode plates are laminated in sequence or a wound structure, wherein the lithium ion originating in the negative electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the negative electrode.
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the negative electrode capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which the positive electrode has a plurality of positive electrode plates, the negative electrode has a plurality of negative electrode plates, and the positive electrode plates, separators and the negative electrode plates are laminated in sequence or a wound structure, wherein the lithium ion originating in the negative electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the negative electrode.
2. The organic electrolytic cell according to claim 1, wherein the active material of the negative electrode is an infusible and insoluble substance having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substance being a heat-treated product of an aromatic condensation polymer.
3. The organic electrolytic cell according to claim 2, wherein the lithium ion is contained in the cell in a total amount of not less than 500 mAh/g and the lithium ion originating in the negative electrode is contained in an amount of not less than 100 mAh/g, based on the active material of the negative electrode.
4. An organic electrolytic cell comprising:
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the positive electrode and an active material of the negative electrode, each capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which the positive electrode has a plurality of positive electrode plates, the negative electrode has a plurality of negative electrode plates, and the positive electrode plates, separators and the negative electrode plates are laminated in sequence or a wound structure, wherein at least one portion of the lithium ion originating in the positive electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the positive electrode.
a positive electrode;
a negative electrode;
a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution;
a current collector of the positive electrode and a current collector of the negative electrode, each provided with pores piercing from a front surface to a back surface;
an active material of the positive electrode and an active material of the negative electrode, each capable of reversibly carrying a lithium ion; and lithium metal arranged to face the negative or positive electrode, wherein the cell has a multi-layer structure in which the positive electrode has a plurality of positive electrode plates, the negative electrode has a plurality of negative electrode plates, and the positive electrode plates, separators and the negative electrode plates are laminated in sequence or a wound structure, wherein at least one portion of the lithium ion originating in the positive electrode is carried through the pores by electrochemical contact with the lithium metal and capable of transferring between the front surface and the back surface of the current collectors, and wherein an opposed area of the lithium metal is not more than 40% of a total area of the positive electrode.
5. The organic electrolytic cell according to claim 4, wherein the active material of the negative electrode is an infusible and insoluble substance having a polyacene skeletal structure and a hydrogen/carbon atomic ratio of 0.50 to 0.05, the substance being a heat-treated product of an aromatic condensation polymer.
6. The organic electrolytic cell according to claim 2 or 3, wherein the aromatic condensation polymer from which the infusible and insoluble substance is obtained is a condensation product of a phenol compound and an aldehyde.
7. The organic electrolytic cell according to any one of claims 1 to 3 or claim 6, wherein the positive electrode comprises an active material selected from the group consisting of:
(1) a lithium-containing metallic oxide capable of electrochemically doping with lithium ion and electrochemically undoping lithium ion; and (2) an oxide of cobalt, manganese or nickel.
(1) a lithium-containing metallic oxide capable of electrochemically doping with lithium ion and electrochemically undoping lithium ion; and (2) an oxide of cobalt, manganese or nickel.
8. The organic electrolytic cell according to any one of claims 1 to 3 or claim 6, wherein the positive electrode comprises an active material which is capable of electrochemically doping with lithium ion and electrochemically undoping lithium ion and is selected from the group consisting of a lithium-containing cobalt oxide, a lithium-containing nickel oxide, and a lithium-containing cobalt-nickel double oxide.
9. The organic electrolytic cell according to any one of claims 1 to 3 or any one of claims 6 to 8, wherein the current collectors of the positive and negative electrodes are made of an expanded metal, a punched metal, a metal net or a foamed metal material, each having a porosity of 10% or more.
10. The organic electrolytic cell according to claim 5, wherein the aromatic condensation polymer from which the infusible and insoluble substance is obtained is a condensation product of a phenol compound and an aldehyde.
11. The organic electrolytic cell according to claim 4, 5 or 10, wherein the positive electrode comprises an active material selected from the group consisting of:
(1) a lithium-containing metallic oxide capable of reversibly carrying lithium, and (2) an oxide or sulfide of a transition metal selected from the group consisting of cobalt, manganese, vanadium, titanium and nickel.
(1) a lithium-containing metallic oxide capable of reversibly carrying lithium, and (2) an oxide or sulfide of a transition metal selected from the group consisting of cobalt, manganese, vanadium, titanium and nickel.
12. The organic electrolytic cell according to claim 4, 5 or 10, wherein the positive electrode comprises an active material that is a lithium-containing metallic oxide capable of reversibly carrying lithium ion, and of emitting lithium ion through an electrochemical oxidation, the lithium-containing metallic oxide being selected from the group consisting of a lithium-containing cobalt oxide, a lithium-containing nickel oxide and a lithium-containing cobalt-nickel double oxide.
13. The organic electrolytic cell according to claim 4 or 5 or 10, wherein the active material of the positive electrode comprises an oxide or sulfide of a transition metal selected from the group consisting of cobalt, manganese, vanadium, titanium and nickel.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2856397 | 1997-01-27 | ||
| JP9/28563 | 1997-01-27 | ||
| JP2974397 | 1997-01-28 | ||
| JP9/29743 | 1997-01-28 | ||
| PCT/JP1998/000187 WO1998033227A1 (en) | 1997-01-27 | 1998-01-20 | Organic electrolytic battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2279864A1 CA2279864A1 (en) | 1998-07-30 |
| CA2279864C true CA2279864C (en) | 2009-02-24 |
Family
ID=26366695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002279864A Expired - Lifetime CA2279864C (en) | 1997-01-27 | 1998-01-20 | Organic electrolytic cell |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6461769B1 (en) |
| EP (1) | EP0964468B1 (en) |
| JP (1) | JP3485935B2 (en) |
| KR (1) | KR100381526B1 (en) |
| CN (1) | CN100380726C (en) |
| AU (1) | AU5497898A (en) |
| CA (1) | CA2279864C (en) |
| DE (2) | DE964468T1 (en) |
| WO (1) | WO1998033227A1 (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6740454B1 (en) * | 1998-07-27 | 2004-05-25 | Kanebo Limited | Organic electrolytic cell with a porous current collector |
| US6757836B1 (en) | 2000-01-10 | 2004-06-29 | Sun Microsystems, Inc. | Method and apparatus for resolving partial connectivity in a clustered computing system |
| US6769008B1 (en) | 2000-01-10 | 2004-07-27 | Sun Microsystems, Inc. | Method and apparatus for dynamically altering configurations of clustered computer systems |
| JP4152084B2 (en) * | 2001-02-27 | 2008-09-17 | 三洋電機株式会社 | Square alkaline storage battery |
| WO2003003395A1 (en) * | 2001-06-29 | 2003-01-09 | Kanebo, Limited | Organic electrolyte capacitor |
| AU2003292614A1 (en) * | 2002-12-25 | 2004-07-22 | Fuji Jukogyo Kabushiki Kaisha | Storage battery |
| WO2004059672A1 (en) * | 2002-12-26 | 2004-07-15 | Fuji Jukogyo Kabushiki Kaisha | Electrical storage device and method for manufacturing electrical storage device |
| WO2004097867A2 (en) * | 2003-03-31 | 2004-11-11 | Kanebo Ltd | Organic electrolyte capacitor |
| KR100863562B1 (en) | 2003-09-30 | 2008-10-15 | 후지 주코교 카부시키카이샤 | Organic electrolytic capacitor |
| KR20070012385A (en) * | 2004-03-31 | 2007-01-25 | 후지 주코교 카부시키카이샤 | Organic electrolyte capacitor using mesoporous carbon material as negative electrode |
| JP4833064B2 (en) * | 2005-03-31 | 2011-12-07 | 富士重工業株式会社 | Lithium ion capacitor |
| JP4731967B2 (en) * | 2005-03-31 | 2011-07-27 | 富士重工業株式会社 | Lithium ion capacitor |
| CN101138058B (en) | 2005-03-31 | 2011-03-30 | 富士重工业株式会社 | Lithium ion capacitor |
| JP4738042B2 (en) * | 2005-03-31 | 2011-08-03 | 旭化成株式会社 | Non-aqueous lithium storage element and method for manufacturing the same |
| WO2006118120A1 (en) | 2005-04-26 | 2006-11-09 | Fuji Jukogyo Kabushiki Kaisha | Negative electrode active material for charging device |
| US7817403B2 (en) | 2005-08-30 | 2010-10-19 | Fuji Jukogyo Kabushiki Kaisha | Lithium ion capacitor |
| JP2007067097A (en) * | 2005-08-30 | 2007-03-15 | Fuji Heavy Ind Ltd | Wound type lithium ion capacitor |
| JP4924966B2 (en) | 2005-10-17 | 2012-04-25 | 富士重工業株式会社 | Lithium ion capacitor |
| JP4813152B2 (en) | 2005-11-14 | 2011-11-09 | 富士重工業株式会社 | Lithium ion capacitor |
| EP1959461A1 (en) * | 2005-11-14 | 2008-08-20 | Matsushita Electric Industrial Co., Ltd. | Electric double layer capacitor |
| JP4842633B2 (en) | 2005-12-22 | 2011-12-21 | 富士重工業株式会社 | Method for producing lithium metal foil for battery or capacitor |
| JP2007180431A (en) * | 2005-12-28 | 2007-07-12 | Fuji Heavy Ind Ltd | Lithium ion capacitor |
| KR100702031B1 (en) * | 2006-02-22 | 2007-03-30 | 삼성전자주식회사 | Semiconductor device with battery |
| JP4971729B2 (en) * | 2006-09-04 | 2012-07-11 | 富士重工業株式会社 | Lithium ion capacitor |
| WO2008049040A2 (en) | 2006-10-17 | 2008-04-24 | Maxwell Technologies, Inc. | Electrode for energy storage device |
| JP4857073B2 (en) * | 2006-10-20 | 2012-01-18 | 富士重工業株式会社 | Lithium ion capacitor |
| JP2008123826A (en) * | 2006-11-10 | 2008-05-29 | Fuji Heavy Ind Ltd | Power storage device |
| JP5214199B2 (en) * | 2007-09-18 | 2013-06-19 | 富士重工業株式会社 | Electricity storage device |
| JP4994205B2 (en) * | 2007-12-06 | 2012-08-08 | 三菱電機株式会社 | Electric double layer capacitor and manufacturing method thereof |
| JP5038954B2 (en) * | 2008-03-26 | 2012-10-03 | 富士重工業株式会社 | Electrode manufacturing method |
| JP2010015974A (en) * | 2008-03-28 | 2010-01-21 | Fuji Heavy Ind Ltd | Manufacturing method of electrode, power storage device, and intermediate laminated material |
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| CN102301439B (en) * | 2008-12-26 | 2014-03-12 | Jm能源股份有限公司 | Wound-type accumulator |
| JP5287317B2 (en) * | 2009-02-10 | 2013-09-11 | 新神戸電機株式会社 | Lithium ion capacitor |
| JP2010205769A (en) * | 2009-02-27 | 2010-09-16 | Fuji Heavy Ind Ltd | Wound-type storage device |
| CN102449811A (en) * | 2009-05-26 | 2012-05-09 | 株式会社Lg化学 | Lithium secondary battery with high energy density |
| KR101861410B1 (en) | 2009-12-28 | 2018-05-28 | 제이에무에나지 가부시키가이샤 | Lithium ion capacitor |
| JP5474622B2 (en) * | 2010-03-24 | 2014-04-16 | 富士重工業株式会社 | Power storage device |
| US8749953B2 (en) | 2010-06-30 | 2014-06-10 | Semiconductor Energy Laboratory Co., Ltd. | Electric double layer capacitor, lithium ion capacitor and manufacturing method thereof |
| EP2605316B8 (en) | 2010-08-11 | 2019-01-23 | KRI, Inc. | Method for lithium predoping, method for producing electrodes, and electric energy storage device using these methods |
| JP5668396B2 (en) * | 2010-10-01 | 2015-02-12 | 新神戸電機株式会社 | Lithium ion storage device |
| US20120236466A1 (en) * | 2011-03-17 | 2012-09-20 | Shin-Kobe Electric Machinery Co., Ltd. | Lithium Ion Capacitor and Layered Member for Lithium Ion Capacitor |
| US20120273255A1 (en) * | 2011-04-26 | 2012-11-01 | Tyco Electronics Corporation | Electrical Conductors Having Organic Compound Coatings |
| KR20140138739A (en) * | 2012-03-29 | 2014-12-04 | 스미토모덴키고교가부시키가이샤 | Electrode material, and capacitor and secondary battery using said electrode material |
| WO2013168727A1 (en) | 2012-05-09 | 2013-11-14 | 株式会社Kri | Predoping method for lithium, lithium-predoped electrode, and electricity storage device |
| JP6161328B2 (en) | 2012-05-18 | 2017-07-12 | Jsr株式会社 | Electrode active material, electrode and power storage device |
| US9461341B2 (en) | 2012-12-26 | 2016-10-04 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for charging the same |
| CN103915262B (en) * | 2013-01-04 | 2017-08-11 | 深圳清华大学研究院 | The method of the pre- embedding lithium of lithium-ion capacitor negative pole |
| JP6294348B2 (en) | 2013-03-11 | 2018-03-14 | エルジー・ケム・リミテッド | Lithium pre-doping method, method for producing lithium secondary battery including this method, and lithium secondary battery produced by this method |
| US20160006034A1 (en) | 2013-03-25 | 2016-01-07 | Jsr Corporation | Electrode active material, electrode and electrical storage device |
| CN105814730B (en) * | 2014-01-06 | 2019-02-26 | 株式会社Lg化学 | Flexible batteries unit |
| US9941506B2 (en) | 2014-02-21 | 2018-04-10 | Semiconductor Energy Laboratory Co., Ltd. | Current collector, secondary battery, electronic device, and manufacturing method thereof |
| CN104037458B (en) * | 2014-05-16 | 2017-02-22 | 中国科学院电工研究所 | Manufacturing method of lithium ion energy storage device |
| JP6630071B2 (en) | 2014-09-01 | 2020-01-15 | Jsr株式会社 | Electrode material, electrode and power storage device |
| CN112018325A (en) | 2014-10-24 | 2020-12-01 | 株式会社半导体能源研究所 | Secondary battery and method for manufacturing secondary battery |
| JP6866202B2 (en) * | 2017-03-28 | 2021-04-28 | 太陽誘電株式会社 | Electrochemical device |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59186274A (en) * | 1983-04-07 | 1984-10-23 | Matsushita Electric Ind Co Ltd | Manufacture of nonaqueous electrolyte secondary battery |
| JPH0789483B2 (en) | 1984-05-07 | 1995-09-27 | 三洋化成工業株式会社 | Secondary battery |
| US5147739A (en) * | 1990-08-01 | 1992-09-15 | Honeywell Inc. | High energy electrochemical cell having composite solid-state anode |
| JPH05266879A (en) * | 1991-05-08 | 1993-10-15 | Unitika Ltd | Composite electrode and battery |
| JPH0541249A (en) * | 1991-08-01 | 1993-02-19 | Toyo Takasago Kandenchi Kk | Lithium secondary battery and method of pouring lithium ion into negative electrode structure for use in lithium battery |
| JP3063320B2 (en) * | 1991-11-25 | 2000-07-12 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| JP3030996B2 (en) * | 1991-11-25 | 2000-04-10 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| JP3030995B2 (en) * | 1991-11-25 | 2000-04-10 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| US5750287A (en) * | 1993-09-22 | 1998-05-12 | Kanebo Ltd. | Organic electrolytic cell |
| JPH08162161A (en) | 1994-12-06 | 1996-06-21 | Kanebo Ltd | Organic electrolytic battery |
| JP2920079B2 (en) * | 1994-12-06 | 1999-07-19 | 鐘紡株式会社 | Organic electrolyte battery |
| JPH08162159A (en) | 1994-12-06 | 1996-06-21 | Kanebo Ltd | Organic elctrolytic battery |
| JP2869354B2 (en) | 1994-12-06 | 1999-03-10 | 鐘紡株式会社 | Organic electrolyte battery |
| US6001139A (en) * | 1995-03-06 | 1999-12-14 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery having multiple-layered negative electrode |
| JP3403856B2 (en) | 1995-03-17 | 2003-05-06 | カネボウ株式会社 | Organic electrolyte battery |
| JP3303694B2 (en) * | 1996-12-17 | 2002-07-22 | 三菱電機株式会社 | Lithium ion secondary battery and method of manufacturing the same |
-
1998
- 1998-01-20 AU AU54978/98A patent/AU5497898A/en not_active Abandoned
- 1998-01-20 EP EP98900431A patent/EP0964468B1/en not_active Expired - Lifetime
- 1998-01-20 DE DE0964468T patent/DE964468T1/en active Pending
- 1998-01-20 US US09/355,164 patent/US6461769B1/en not_active Expired - Lifetime
- 1998-01-20 JP JP53181198A patent/JP3485935B2/en not_active Expired - Lifetime
- 1998-01-20 DE DE69837838T patent/DE69837838T2/en not_active Expired - Lifetime
- 1998-01-20 WO PCT/JP1998/000187 patent/WO1998033227A1/en active IP Right Grant
- 1998-01-20 CA CA002279864A patent/CA2279864C/en not_active Expired - Lifetime
- 1998-01-20 CN CNB988020653A patent/CN100380726C/en not_active Expired - Lifetime
- 1998-01-20 KR KR10-1999-7006773A patent/KR100381526B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| JP3485935B2 (en) | 2004-01-13 |
| EP0964468A4 (en) | 2004-09-29 |
| CN1244954A (en) | 2000-02-16 |
| DE69837838D1 (en) | 2007-07-12 |
| KR100381526B1 (en) | 2003-04-23 |
| CN100380726C (en) | 2008-04-09 |
| KR20000070528A (en) | 2000-11-25 |
| EP0964468B1 (en) | 2007-05-30 |
| CA2279864A1 (en) | 1998-07-30 |
| EP0964468A1 (en) | 1999-12-15 |
| DE69837838T2 (en) | 2008-01-31 |
| AU5497898A (en) | 1998-08-18 |
| DE964468T1 (en) | 2000-06-08 |
| WO1998033227A1 (en) | 1998-07-30 |
| US6461769B1 (en) | 2002-10-08 |
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