CA2610077A1 - Lithium manganese compounds and methods of making the same - Google Patents
Lithium manganese compounds and methods of making the same Download PDFInfo
- Publication number
- CA2610077A1 CA2610077A1 CA002610077A CA2610077A CA2610077A1 CA 2610077 A1 CA2610077 A1 CA 2610077A1 CA 002610077 A CA002610077 A CA 002610077A CA 2610077 A CA2610077 A CA 2610077A CA 2610077 A1 CA2610077 A1 CA 2610077A1
- Authority
- CA
- Canada
- Prior art keywords
- lithium metal
- compound
- mixing
- lithium
- limn2o4
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 39
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical class [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 35
- -1 MnO2 compound Chemical class 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 5
- 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
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims 4
- 238000000498 ball milling Methods 0.000 claims 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 150000002697 manganese compounds Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910003007 LixMnO2 Inorganic materials 0.000 abstract description 8
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 229910052596 spinel Inorganic materials 0.000 description 18
- 239000011029 spinel Substances 0.000 description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910010077 Li2MnO2 Inorganic materials 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 7
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 7
- 101150073459 UROS gene Proteins 0.000 description 6
- 229910002993 LiMnO2 Inorganic materials 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 229910010226 Li2Mn2O4 Inorganic materials 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910006570 Li1+xMn2-xO4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
Abstract
Electrode materials such as LixMnO2 where 0.2 < x <= 2 compounds for use with rechargeable lithium ion batteries can be formed by mixing LiMn2O4 compounds or manganese dioxide compounds with lithium metal or stabilized and non-stabilized lithium metal powders.
Description
LITHIUM MANGANESE COMPOUNDS
AND METHODS OF MAKING THE SAME
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Application Serial Number 60/695,159, filed June 29, 2005, the disclosure of which is incorporated by reference in its entirety.
FIELD OF THE INVENTION
AND METHODS OF MAKING THE SAME
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Application Serial Number 60/695,159, filed June 29, 2005, the disclosure of which is incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention generally relates to methods for forming lithium compounds, and the compounds formed by such methods. More particularly, this invention relates to methods for forming lithium manganese compounds and doped lithium manganese conipounds by lithiation techniques.
BACKGROUND OF THE INVENTION
BACKGROUND OF THE INVENTION
[0003] Attractive materials for use as cathode materials for lithium ion secondary batteries include LiCoO2, LiNiOa, and LiMn2O4. Unlike LiCoO2 and LiNiO2, the LiMnaO4 spinel compounds are believed to be overcharge safer and are desirable cathode materials for that reason. Nevertheless, although cycling over the full capacity range for pure LiMn2O4 can be done safely, the specific capacity of LiMn2O4 is low. Specifically, the theoretical capacity of LiMn2O4 is only 148 mA=hr/g and typically no more than about 115-120 mA=hr/g can be obtained with good cycleability. LiMn2O4 can contain excess lithium on the 16d manganese sites and can be written as Li1+XMn2-XO4 (05 x_< 0.33). Use of the formula LiMn2O4 herein is understood to denote Li1+XMn2_,tO4 as well.
[0004] The orthorhombic LiMnOa and the tetragonally distorted spinel Li2Mn2O4 have the potential for larger capacities than those obtained with the LiMn2O4 spinel.
However, cycling over the full capacity range for LiMnO2 and Li2Mn2O4 results in a rapid capacity fade. Layered LiMnO2 quickly converts to a spinel form upon cycling which also results in a capacity fade.
However, cycling over the full capacity range for LiMnO2 and Li2Mn2O4 results in a rapid capacity fade. Layered LiMnO2 quickly converts to a spinel form upon cycling which also results in a capacity fade.
[0005] Various attempts have been made to either improve the specific capacity or safety of the lithium metal oxides used in secondary lithium batteries by doping these lithium metal oxides with other cations. For example, U.S. Patent No. 6,214,493 to Bruce et al.
relates to stabilized layered LiMnO2 using cobalt (Co) as a dopant material.
Stabilization has been recorded with as little as 15 percent cobalt substitution. In another example, U.S. Patent No. 5,370,949 to Davidson et al. proposes that introducing chromium cations into LiMnO2 can produce a tetragonally distorted spinel type of structure which is air stable and has good reversibility on cycling in lithium cells.
relates to stabilized layered LiMnO2 using cobalt (Co) as a dopant material.
Stabilization has been recorded with as little as 15 percent cobalt substitution. In another example, U.S. Patent No. 5,370,949 to Davidson et al. proposes that introducing chromium cations into LiMnO2 can produce a tetragonally distorted spinel type of structure which is air stable and has good reversibility on cycling in lithium cells.
[0006] Li2MnO2 compounds have also been considered as electrode materials.
U.S. Patent No. 4,980,251 to Thackeray proposes that Li2MnO2 can be formed having a theoretical capacity of 530 mA=hr/g by reacting LiMn2O4 spinel compounds with n-BuLi as follows:
LiMn2O4 + n-BuLi -+ Li2Mn2O4 + 2n-BuLi -~ 2 Li2MnO2 The Li2MnO2 has a hexagonal close packed layered structure, similar to the structure of LiCoO2, except that the Li+ ions in Li2MnO2 occupy the tetrahedral sites instead of the octahedral sites as in LiCoO2. However, the Li2MnO2 compounds formed according to Thackeray's methods are unstable. In particular, Thackeray notes that the layered structure of Li2MnO2 is unstable and that it converts back to the spinel framework upon delithiation.
This is undesirable because repeated conversion between layered and spinel structures decreases capacity retention and results in voltage gaps.
U.S. Patent No. 4,980,251 to Thackeray proposes that Li2MnO2 can be formed having a theoretical capacity of 530 mA=hr/g by reacting LiMn2O4 spinel compounds with n-BuLi as follows:
LiMn2O4 + n-BuLi -+ Li2Mn2O4 + 2n-BuLi -~ 2 Li2MnO2 The Li2MnO2 has a hexagonal close packed layered structure, similar to the structure of LiCoO2, except that the Li+ ions in Li2MnO2 occupy the tetrahedral sites instead of the octahedral sites as in LiCoO2. However, the Li2MnO2 compounds formed according to Thackeray's methods are unstable. In particular, Thackeray notes that the layered structure of Li2MnO2 is unstable and that it converts back to the spinel framework upon delithiation.
This is undesirable because repeated conversion between layered and spinel structures decreases capacity retention and results in voltage gaps.
[0007] A doped lithium manganese oxide preferably exhibits a high usable reversible capacity and good cycleability to maintain reversible capacity during cycling.
LiMn2O4 can generally only be operated at 115-120 mA=hr/g with good cycleability.
Furthermore, Li2MnO2 compounds are expensive to make and are unstable when made according to available methods. Therefore, there is a need to produce a lithium metal oxide that exhibits an improved reversible capacity and good cycleability while maintaining thermal stability.
SUMMARY OF THE INVENTION
LiMn2O4 can generally only be operated at 115-120 mA=hr/g with good cycleability.
Furthermore, Li2MnO2 compounds are expensive to make and are unstable when made according to available methods. Therefore, there is a need to produce a lithium metal oxide that exhibits an improved reversible capacity and good cycleability while maintaining thermal stability.
SUMMARY OF THE INVENTION
[0008] Embodiments of the present invention include methods for making lithium manganese oxide compounds and doped lithium manganese oxide compounds. The lithium manganese compounds and doped lithium manganese oxide compounds formed according to embodiments of the present invention can be used to form electrodes and electrode materials for use in batteries, such as rechargeable lithium ion batteries.
[0009] According to some embodiments of the present invention, a doped lithium manganese spinel compound is mixed with lithium metal to produce a doped LiXMnO2 compound where 0.2 < x<_ 2. The mixing of the spinel compound and lithium metal can be performed with or without a solvent. Mixing of the spinel compound and lithium metal can be performed using processes capable of energetically mixing the doped lithium manganese spinel compound and lithium metal, such as by high energy ball milling. The mixing preferably provides as much contact between the spinel compound and the lithium metal as possible. A doped lithium manganese spinel compound can include compounds such as those disclosed by U.S. Patent No. 6,267,943 to Manev et al., which is incorporated in its entirety herein by reference. The lithium metal is preferably a stabilized lithium metal powder such as those disclosed by U.S. Patent Nos. 5,567,474 and 5,776,369 to Dover et al., which are incorporated herein by reference in their entireties. One of the added advantages of the present invention is that the amount of lithium x in LiXMnOa, where 0.2 < x_ 2, can be easily controlled and varied by varying the amount of the lithium metal used in synthesis, unlike high temperature solid state synthesis where the x value is governed by the high temperature phase diagram and may not be changed at will.
[0010] In other embodiments of the present invention, a manganese dioxide such as a heat treated electrolytic manganese dioxide (EMD) compound can be mixed with a lithium metal to lithiate the manganese dioxide compound. The lithiated manganese dioxide such as the lithiated EMD material can be used as an electrode material in rechargeable lithium ion batteries. The lithium metal powder is preferably a stabilized lithium metal powder such as those disclosed by U.S. Patent Nos. 5,567,474 and 5,776,369 to Dover et al.
[0011] Electrodes for use in batteries, and particularly for use with rechargeable lithium ion cell batteries, can be formed using the Li,,MnO2 where 0.2 < x<_ 2 compounds or lithiated EMD materials formed according to embodiments of the present invention.
[0012] The foregoing and other aspects of the present invention are explained in greater detail in the specification set forth below and will be apparent from the description of the invention and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[00131 Figure 1 is a graphic comparison of x-ray diffraction patterns according to Example 1.
[0014] Figure 2 is a graphic comparison of x-ray diffraction patterns according to Example 2 and Comparative Example 1.
~
[0015] Figure 3 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 2.
[0016] Figure 4 is a graphic comparison of x-ray diffraction patterns according to Examples 3 and 4, and Comparative Example 1.
[0017] Figure 5 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention now will be described more fully hereinafter.
This invention may, however, be embodied in many different fonns and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0019] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Additionally, as used herein, the term "and/or"
includes any and all combinations of one or more of the associated listed items.
[0020] Unless otherwise defmed, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
[0021] All publications, U.S. patent applications, U.S. patents and other references cited herein are incorporated by reference in their entireties.
[0022] Embodiments of the present invention include methods for making lithium manganese oxide compounds and doped lithium manganese oxide compounds. The lithium manganese compounds and doped lithium manganese oxide compounds formed according to embodiments of the present invention can be used to form electrodes and electrode materials for use in batteries, such as rechargeable lithium ion batteries.
[0023] According to embodiments of the present invention, methods for forming a lithium manganese oxide compound having the formula LiXMnO2 where 0.2 < x_ 2 are provided. In some embodiments, the lithium manganese oxide compound can be a doped lithium manganese oxide compound. For example, a doped lithium manganese oxide compound having the formula Li2Mnl_,A,O2 can be formed, wherein A is a dopant and 0<_ a 0.5.
[0024] A lithium manganese oxide compound having the formula LixMnOa where 0.2 < x S 2, often 0.5 < x_ 2 can be formed according to embodiments of the present invention by mixing an LiMn2O4 spinel compound with lithium metal. As the LiMn2O4 compound comes in contact with the lithium metal, the compound accepts the lithium and converts to the desired LiXMnO2 coinpound. For example, an LiMn2O4 compound can be mixed with lithium metal in a ball mill to form LiXMnO2. The lithium metal is preferably a stabilized lithium metal powder. The mixing of the LiMn2O4 compound can be performed using any mixing techniques, however, mixing that improves the amount of contact between the LiMn2O4 compound and the lithium metal is preferred.
[0025] The lithium metal in one embodiment, can be added all at once. In another embodiment, the lithium is added in smaller increments, e.g. x/4 or less. Such addition avoids distortion of the x-ray diffraction pattern, and allows the LiXMnO2 compound to maintain an x-ray diffraction (crystallinity) pattern similar to that of EMD.
[0026] The lithium metal used with embodiments of the present invention can include stabilized lithium metal powder ("SLMP"). For example, FMC Corporation produces a stabilized lithium metal powder under the name Lectro Max Powder that may be used with embodiments of the present invention. Other lithium metal powders may also be used.
For instance, U.S. Patent No. 5,567,474 and U.S. Patent No. 5,776,369, describe stabilized lithium metal powders and processes for making such powders that can be used with the embodiments of the present invention.
[00271 Stabilized lithium metal powders allow the methods of embodiments of the present invention to be performed with increased safety. However, lithium metal powders that are not stabilized can also be used with embodiments of the present invention. In those embodiments where non-stabilized lithium metal or lithium metal powders are used, additional processes can be employed to improve the safety of the reactions.
For example, the mixing of an LiMn2O4 compound with the non-stabilized lithium metal or lithium metal powder can be performed in an inert atmosphere to inhibit undesired reactions of the lithium metal with the atmosphere.
[0028] In other embodiments of the present invention, a doped LiMnO2 compound can be formed by mixing a doped LiMn2O4 compound with lithium metal.
The doped LiMn2O4 compounds can include LiMn2O4 compounds doped with dopants such as cobalt (Co), nickel (Ni), magnesium (Mg), titanium (Ti), zirconium (Zr), chromium (Cr), or other dopants used in the production of electrode materials for use with batteries and rechargeable lithium-ion batteries. The lithium metal is preferably a stabilized lithium metal powder.
[0029] The mixing of lithium metal with LiMn2O4 or doped LiMn2O4 spinel compounds can be performed in a ball mill or according to other mixing techniques. In some embodiments, the mixing preferably includes energetic mixing which increases the mixing of the compounds, improving the amount of contact between the LiMn2O4 compounds and the lithium metal. , [0030] The mixing of lithium metal with LiMn2O4 can be performed with or without a solvent. If a solvent is used, the solvent is preferably compatible with lithium such that the lithium metal does not react with the solvent during the mixing.
Solvents that can be used with embodiments of the present invention include, but are not limited to, acyclic and cyclic hydrocarbons, including n-hexane, n-heptane, cyclohexane, and the like;
aromatic hydrocarbons such as toluene, xylene, isopropylbenzene (cumene), and the like;
symmetrical, unsymmetrical, and cyclic ethers, including di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran, and the like.
[0031] In some embodiments of the present invention, the LiMnZO4 compounds can be produced by calcining a mixture of at least one manganese oxide, at least one lithium compound, and optionally at least one dopant in a firing step at a temperature between 400 C
and 900 C. The manganese oxide compounds can include such compounds as Mn203, Mn304, electrolytic manganese dioxide, and (3-Mn02, and the firing step can include multiple firing steps.
[0032] In the calcining step, the mixture of source compounds is fired at between about 400 C and about 900 C. Preferably, the mixture is calcined using more than one firing step at firing temperature with this temperature range. During calcinations, agglomeration of the spinel particles is preferably prevented. For example, during a multiple step firing sequence, agglomeration can be prevented by firing the source compounds in a fluid bed furnace or rotary calciner during at least a portion of the firing steps or by grinding the spinel material between steps.
[0033] The manganese oxide compounds produced in this manner can be formed into LiMnaO4 compounds that can be used with embodiments of the present invention. In addition, other methods for forming lithium manganese oxides may be used with embodiments of the present invention. For instance, the inethods and compounds of U.S.
Patent Numbers 6,267,943; 6,423,294; and 6,517,803 may be used with embodiments of the present invention.
[0034] The lithiated EMD materials formed according to embodiments of the present invention exhibit a capacity of about 150 mA-hr/g to about 160 mA=hr/g when incorporated into an electrode. In addition, the lithiated EMD materials of the present invention can be made cheaply because EMD compounds are readily available and easily produced.
[0035] According to some embodiments of the present invention, the lithiated EMD materials of the present invention can be used as low cost materials for forming electrodes for use with lithium ion batteries.
[0036] Embodiments of the invention also include batteries and electrodes formed from compounds and materials produced according to embodiments of the present invention.
An electrode for use with a lithium ion battery can be formed from the LiXMnOa compounds or doped LiXMnO2 compounds formed according to embodiments of the present invention. In .
addition, the lithiated EMD materials formed according to embodiments of the present invention can be used to form electrodes for use in lithium ion batteries. The LiXMnO2 compounds and lithiated EMD materials formed according to embodiments of the present invention can be used to form anodes or cathodes for use in batteries and especially for use with rechargeable lithium ion batteries.
[0037] Having now described the invention, the same will be illustrated with reference to certain examples, wliich are included herein for illustration purposes only, and which are not intended to be limiting of the invention.
EXAMPLES
Example 1 Lithium is added into a heat treated electrolytic manganese dioxide ("HEMD").
Electrolytic manganese dioxide available for Erachem-Comilog was ground to reduce the particle size and heat treated at 400oC for 12 hours to obtaind heat treated electrolytic manganese. The lithium is added in small increments of 0.075 moles of Li per one mole of manganese oxide. The addition is done in glove box at room temperature and stainless steel ball mill jar is used as a mixing vessel.
Figure 1 shows the x-ray diffraction patters of HEMD with no lithium and the various total addition amounts (0.30 moles Li to 0.58 moles Li). Comparison of the x-ray diffraction patterns demonstrates that the lithium can be added incrementally without distorting the structure of the HEMD to maintain the HEMD-like structure.
Example 2 and Comparative Example 1 Lio,3MnO2 is prepared by two ways. In Comparative Example 1, all 0.3 moles of lithium to one mole manganese oxide are added at once. In Example 2, the lithium is added in increments of 0.075 moles lithium to one mole manganese oxide.
The x-ray diffraction pattern of Figure 2 shows a well crystalline spinel-like structure for the Li0.3MnO2 of Comparative Example 1. This is contrasted to the x-ray diffraction pattern for Example 2 which shows a pattern similar to that of the HEMD raw material sample and graphically indicates very little distortion therefrom.
Figure 3 shows electrochemical results. The Li0.3MnO2 of Example 2 shows an increase of first charge efficiency from 45 percent to 93 percent as compared to the one-step addition process of Comparative Example 1. The voltage profile was sustained for over 10 cycles which implies no structural changes occurred. Such sustaining of the voltage profile indicates such a material is a good candidate for 3V rechargeable lithium batteries.
Examples 3 and 4 and Comparative Example 2 Lio66MnO2 is prepared by three ways. In Comparative Example 2, all of the 0.6 moles of lithium to one mole of manganese oxide are added at once. In Example 3, the 0.6 moles of lithium to one mole of manganese oxide are added in increments of 0.15 moles.
In Example 4, the litliium is added in increments of 0.075 moles of lithium to one mole of manganese oxide.
The x-ray diffraction pattern for Comparative Example 2 in Figure 4 shows a well-crystalline spinel-like structure for the Li066MnO2 but is distorted as compared to the HEMD
raw material sample. This is contrasted to Examples 3 and 4 which show patterns similar to that of the HEMD raw material sample and indicates very little distortion.
Figure 5 shows electrochemical results. The Li0.6MnO2 of Example 3 shows an increase of first charge efficiency from 39 percent to 81 percent as compared to the one-step addition process of Comparative Example 2.
[0038] Having thus described certain embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof as hereinafter claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[00131 Figure 1 is a graphic comparison of x-ray diffraction patterns according to Example 1.
[0014] Figure 2 is a graphic comparison of x-ray diffraction patterns according to Example 2 and Comparative Example 1.
~
[0015] Figure 3 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 2.
[0016] Figure 4 is a graphic comparison of x-ray diffraction patterns according to Examples 3 and 4, and Comparative Example 1.
[0017] Figure 5 is a graph of Voltage (V) versus Specific Capacity (mAH/g) relating to Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention now will be described more fully hereinafter.
This invention may, however, be embodied in many different fonns and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0019] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Additionally, as used herein, the term "and/or"
includes any and all combinations of one or more of the associated listed items.
[0020] Unless otherwise defmed, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
[0021] All publications, U.S. patent applications, U.S. patents and other references cited herein are incorporated by reference in their entireties.
[0022] Embodiments of the present invention include methods for making lithium manganese oxide compounds and doped lithium manganese oxide compounds. The lithium manganese compounds and doped lithium manganese oxide compounds formed according to embodiments of the present invention can be used to form electrodes and electrode materials for use in batteries, such as rechargeable lithium ion batteries.
[0023] According to embodiments of the present invention, methods for forming a lithium manganese oxide compound having the formula LiXMnO2 where 0.2 < x_ 2 are provided. In some embodiments, the lithium manganese oxide compound can be a doped lithium manganese oxide compound. For example, a doped lithium manganese oxide compound having the formula Li2Mnl_,A,O2 can be formed, wherein A is a dopant and 0<_ a 0.5.
[0024] A lithium manganese oxide compound having the formula LixMnOa where 0.2 < x S 2, often 0.5 < x_ 2 can be formed according to embodiments of the present invention by mixing an LiMn2O4 spinel compound with lithium metal. As the LiMn2O4 compound comes in contact with the lithium metal, the compound accepts the lithium and converts to the desired LiXMnO2 coinpound. For example, an LiMn2O4 compound can be mixed with lithium metal in a ball mill to form LiXMnO2. The lithium metal is preferably a stabilized lithium metal powder. The mixing of the LiMn2O4 compound can be performed using any mixing techniques, however, mixing that improves the amount of contact between the LiMn2O4 compound and the lithium metal is preferred.
[0025] The lithium metal in one embodiment, can be added all at once. In another embodiment, the lithium is added in smaller increments, e.g. x/4 or less. Such addition avoids distortion of the x-ray diffraction pattern, and allows the LiXMnO2 compound to maintain an x-ray diffraction (crystallinity) pattern similar to that of EMD.
[0026] The lithium metal used with embodiments of the present invention can include stabilized lithium metal powder ("SLMP"). For example, FMC Corporation produces a stabilized lithium metal powder under the name Lectro Max Powder that may be used with embodiments of the present invention. Other lithium metal powders may also be used.
For instance, U.S. Patent No. 5,567,474 and U.S. Patent No. 5,776,369, describe stabilized lithium metal powders and processes for making such powders that can be used with the embodiments of the present invention.
[00271 Stabilized lithium metal powders allow the methods of embodiments of the present invention to be performed with increased safety. However, lithium metal powders that are not stabilized can also be used with embodiments of the present invention. In those embodiments where non-stabilized lithium metal or lithium metal powders are used, additional processes can be employed to improve the safety of the reactions.
For example, the mixing of an LiMn2O4 compound with the non-stabilized lithium metal or lithium metal powder can be performed in an inert atmosphere to inhibit undesired reactions of the lithium metal with the atmosphere.
[0028] In other embodiments of the present invention, a doped LiMnO2 compound can be formed by mixing a doped LiMn2O4 compound with lithium metal.
The doped LiMn2O4 compounds can include LiMn2O4 compounds doped with dopants such as cobalt (Co), nickel (Ni), magnesium (Mg), titanium (Ti), zirconium (Zr), chromium (Cr), or other dopants used in the production of electrode materials for use with batteries and rechargeable lithium-ion batteries. The lithium metal is preferably a stabilized lithium metal powder.
[0029] The mixing of lithium metal with LiMn2O4 or doped LiMn2O4 spinel compounds can be performed in a ball mill or according to other mixing techniques. In some embodiments, the mixing preferably includes energetic mixing which increases the mixing of the compounds, improving the amount of contact between the LiMn2O4 compounds and the lithium metal. , [0030] The mixing of lithium metal with LiMn2O4 can be performed with or without a solvent. If a solvent is used, the solvent is preferably compatible with lithium such that the lithium metal does not react with the solvent during the mixing.
Solvents that can be used with embodiments of the present invention include, but are not limited to, acyclic and cyclic hydrocarbons, including n-hexane, n-heptane, cyclohexane, and the like;
aromatic hydrocarbons such as toluene, xylene, isopropylbenzene (cumene), and the like;
symmetrical, unsymmetrical, and cyclic ethers, including di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran, and the like.
[0031] In some embodiments of the present invention, the LiMnZO4 compounds can be produced by calcining a mixture of at least one manganese oxide, at least one lithium compound, and optionally at least one dopant in a firing step at a temperature between 400 C
and 900 C. The manganese oxide compounds can include such compounds as Mn203, Mn304, electrolytic manganese dioxide, and (3-Mn02, and the firing step can include multiple firing steps.
[0032] In the calcining step, the mixture of source compounds is fired at between about 400 C and about 900 C. Preferably, the mixture is calcined using more than one firing step at firing temperature with this temperature range. During calcinations, agglomeration of the spinel particles is preferably prevented. For example, during a multiple step firing sequence, agglomeration can be prevented by firing the source compounds in a fluid bed furnace or rotary calciner during at least a portion of the firing steps or by grinding the spinel material between steps.
[0033] The manganese oxide compounds produced in this manner can be formed into LiMnaO4 compounds that can be used with embodiments of the present invention. In addition, other methods for forming lithium manganese oxides may be used with embodiments of the present invention. For instance, the inethods and compounds of U.S.
Patent Numbers 6,267,943; 6,423,294; and 6,517,803 may be used with embodiments of the present invention.
[0034] The lithiated EMD materials formed according to embodiments of the present invention exhibit a capacity of about 150 mA-hr/g to about 160 mA=hr/g when incorporated into an electrode. In addition, the lithiated EMD materials of the present invention can be made cheaply because EMD compounds are readily available and easily produced.
[0035] According to some embodiments of the present invention, the lithiated EMD materials of the present invention can be used as low cost materials for forming electrodes for use with lithium ion batteries.
[0036] Embodiments of the invention also include batteries and electrodes formed from compounds and materials produced according to embodiments of the present invention.
An electrode for use with a lithium ion battery can be formed from the LiXMnOa compounds or doped LiXMnO2 compounds formed according to embodiments of the present invention. In .
addition, the lithiated EMD materials formed according to embodiments of the present invention can be used to form electrodes for use in lithium ion batteries. The LiXMnO2 compounds and lithiated EMD materials formed according to embodiments of the present invention can be used to form anodes or cathodes for use in batteries and especially for use with rechargeable lithium ion batteries.
[0037] Having now described the invention, the same will be illustrated with reference to certain examples, wliich are included herein for illustration purposes only, and which are not intended to be limiting of the invention.
EXAMPLES
Example 1 Lithium is added into a heat treated electrolytic manganese dioxide ("HEMD").
Electrolytic manganese dioxide available for Erachem-Comilog was ground to reduce the particle size and heat treated at 400oC for 12 hours to obtaind heat treated electrolytic manganese. The lithium is added in small increments of 0.075 moles of Li per one mole of manganese oxide. The addition is done in glove box at room temperature and stainless steel ball mill jar is used as a mixing vessel.
Figure 1 shows the x-ray diffraction patters of HEMD with no lithium and the various total addition amounts (0.30 moles Li to 0.58 moles Li). Comparison of the x-ray diffraction patterns demonstrates that the lithium can be added incrementally without distorting the structure of the HEMD to maintain the HEMD-like structure.
Example 2 and Comparative Example 1 Lio,3MnO2 is prepared by two ways. In Comparative Example 1, all 0.3 moles of lithium to one mole manganese oxide are added at once. In Example 2, the lithium is added in increments of 0.075 moles lithium to one mole manganese oxide.
The x-ray diffraction pattern of Figure 2 shows a well crystalline spinel-like structure for the Li0.3MnO2 of Comparative Example 1. This is contrasted to the x-ray diffraction pattern for Example 2 which shows a pattern similar to that of the HEMD raw material sample and graphically indicates very little distortion therefrom.
Figure 3 shows electrochemical results. The Li0.3MnO2 of Example 2 shows an increase of first charge efficiency from 45 percent to 93 percent as compared to the one-step addition process of Comparative Example 1. The voltage profile was sustained for over 10 cycles which implies no structural changes occurred. Such sustaining of the voltage profile indicates such a material is a good candidate for 3V rechargeable lithium batteries.
Examples 3 and 4 and Comparative Example 2 Lio66MnO2 is prepared by three ways. In Comparative Example 2, all of the 0.6 moles of lithium to one mole of manganese oxide are added at once. In Example 3, the 0.6 moles of lithium to one mole of manganese oxide are added in increments of 0.15 moles.
In Example 4, the litliium is added in increments of 0.075 moles of lithium to one mole of manganese oxide.
The x-ray diffraction pattern for Comparative Example 2 in Figure 4 shows a well-crystalline spinel-like structure for the Li066MnO2 but is distorted as compared to the HEMD
raw material sample. This is contrasted to Examples 3 and 4 which show patterns similar to that of the HEMD raw material sample and indicates very little distortion.
Figure 5 shows electrochemical results. The Li0.6MnO2 of Example 3 shows an increase of first charge efficiency from 39 percent to 81 percent as compared to the one-step addition process of Comparative Example 2.
[0038] Having thus described certain embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof as hereinafter claimed.
Claims (22)
1. A method for forming Li x MnO2, comprising mixing an LiMn2O4 compound with lithium metal to form Li x MnO2 where 0.2 < × <= 2 wherein the crystalline structure of the Li x Mn2O4 compound is maintained.
2. The method of claim 1, wherein the Li x MnO2 compound is doped with a dopant selected from the group consisting of cobalt, nickel, titanium, zirconium, and chromium.
3. The method of claim 1, wherein the lithium metal comprises a lithium metal powder.
4. The method of claim 3, wherein the lithium metal powder comprises a stabilized lithium metal powder.
5. The method of Claim 1 wherein the lithium metal is added in one quarter increments of x or less.
6. The method of claim 5, wherein mixing the Li x MnO2 compound is formed by energetically mixing a LiMn2O4 compound with lithium metal in a ball mill.
7. The method of claim 5, wherein the ball mill is a high energy ball mill.
8. The method of claim 6, wherein mixing the LiMn2O4 compound with lithium metal further comprises mixing the LiMn2O4 compound with the lithium metal in the presence of a solvent.
9. The method of claim 8, wherein the solvent comprises a solvent selected from the group consisting of acyclic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, symmetrical ethers, unsymmetrical ethers, and cyclic ethers.
10. An electrode formed from the Li x MnO2 compound formed according to the method of claim 1.
11. An electrode, comprising an Li x MnO2 where 0.2 < × <= 2 compound formed by mixing an LiMn2O4 compound with lithium metal wherein the crystalline structure of the LiMn2O4 compound is maintained.
12. The electrode of claim 11, wherein the lithium metal comprises a lithium metal powder.
13. The electrode of claim 12, wherein the lithium metal powder comprises a stabilized lithium metal powder.
14. The method of Claim 11 wherein the lithium metal is added in one quarter increments of x or less.
15. A method of forming a lithiated electrode material, comprising mixing an electrolytic manganese dioxide (EMD) compound with lithium metal to produce a lithiated electrolytic manganese dioxide material wherein the crystalline structure of the EMD
compound is maintained.
compound is maintained.
16. The method of claim 15, wherein the lithium metal comprises a lithium metal powder.
17. The method of claim 15, wherein the lithium metal powder comprises a stabilized lithium metal powder.
18. The method of claim 15, wherein the electrolytic manganese dioxide compound comprises a heat treated electrolytic manganese dioxide compound.
19. The method of claim 15, wherein mixing the electrolytic manganese dioxide compound with lithium metal comprises ball milling the electrolytic manganese dioxide compound with lithium metal wherein the lithium metal is incrementally added.
20. The method of claim 19, wherein ball milling the electrolytic manganese dioxide compound with lithium metal further comprises ball milling the electrolytic manganese dioxide compound with lithium metal in the presence of a solvent.
21. The method of claim 20, wherein the solvent is selected from the group consisting of acyclic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, symmetrical ethers, unsymmetrical ethers, and cyclic ethers.
22. The method of Claim 20, wherein the electrolytic manganese compound is doped with a dopant selected from the group consisting of cobalt, nickel, titanium, zirconium, and chromium and any combinations thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2840566A CA2840566C (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69515905P | 2005-06-29 | 2005-06-29 | |
US60/695,159 | 2005-06-29 | ||
PCT/US2006/025694 WO2007002907A2 (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2840566A Division CA2840566C (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2610077A1 true CA2610077A1 (en) | 2007-01-04 |
CA2610077C CA2610077C (en) | 2014-04-08 |
Family
ID=37596079
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2610077A Expired - Fee Related CA2610077C (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
CA2840566A Expired - Fee Related CA2840566C (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2840566A Expired - Fee Related CA2840566C (en) | 2005-06-29 | 2006-06-29 | Lithium manganese compounds and methods of making the same |
Country Status (10)
Country | Link |
---|---|
US (3) | US7771874B2 (en) |
EP (1) | EP1896366B1 (en) |
JP (1) | JP5096329B2 (en) |
KR (2) | KR101368855B1 (en) |
CN (1) | CN101213146B (en) |
CA (2) | CA2610077C (en) |
DE (1) | DE112006001610B4 (en) |
GB (1) | GB2439890B (en) |
RU (1) | RU2007149066A (en) |
WO (1) | WO2007002907A2 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0423194D0 (en) | 2004-10-19 | 2004-11-24 | Racal Acoustics Ltd | Attachment apparatus |
US7771874B2 (en) * | 2005-06-29 | 2010-08-10 | Fmc Corporation | Lithium manganese compounds and methods of making the same |
KR100786968B1 (en) * | 2005-07-22 | 2007-12-17 | 주식회사 엘지화학 | Pre-treatment method of electrode active material |
TWI330419B (en) | 2005-08-19 | 2010-09-11 | Lg Chemical Ltd | Electrochemical device with high capacity and method for preparing the same |
US8282856B2 (en) * | 2010-05-28 | 2012-10-09 | Harmony Brother Co., Ltd. | Method for sintering lithium contained electrode material |
KR101771279B1 (en) * | 2010-08-11 | 2017-08-24 | 가부시끼가이샤 케이알아이 | Method for lithium predoping, method for producing electrodes, and electric energy storage device using these methods |
JP5714262B2 (en) * | 2010-08-11 | 2015-05-07 | 株式会社Kri | Lithium pre-doping method, electrode manufacturing method, and electricity storage device using these methods |
JP5714283B2 (en) * | 2010-09-28 | 2015-05-07 | 株式会社Kri | Pre-doped electrode manufacturing method and power storage device |
CN102205989A (en) * | 2011-03-25 | 2011-10-05 | 江苏国泰锂宝新材料有限公司 | Preparation method for cathode material LiMn2O4 of cell |
JP2012204310A (en) * | 2011-03-28 | 2012-10-22 | Kri Inc | Lithium pre-doping method, manufacturing method of electrode, and power storage device made using the methods |
JP5792975B2 (en) * | 2011-03-28 | 2015-10-14 | 株式会社Kri | Lithium pre-doping method |
JP6156078B2 (en) | 2013-11-12 | 2017-07-05 | 日亜化学工業株式会社 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
JP6524651B2 (en) | 2013-12-13 | 2019-06-05 | 日亜化学工業株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same |
US9711792B2 (en) | 2014-03-10 | 2017-07-18 | Hitachi, Ltd. | Positive electrode active material for secondary batteries and lithium ion secondary battery using the same |
US9979011B2 (en) * | 2014-09-26 | 2018-05-22 | The United States Of America As Represented By The Secretary Of The Army | LixMn2O4-y(C1z) spinal cathode material, method of preparing the same, and rechargeable lithium and li-ion electrochemical systems containing the same |
US10505188B2 (en) * | 2015-03-03 | 2019-12-10 | The Government Of The United States As Represented By The Secretary Of The Army | “B” and “O” site doped AB2O4 spinel cathode material, method of preparing the same, and rechargeable lithium and Li-ion electrochemical systems containing the same |
KR101681545B1 (en) | 2015-05-18 | 2016-12-01 | 서울대학교산학협력단 | Positive electrode active material for rechargable lithium battery, method for manufacturing the same, and rechargable lithium battery including the same |
US10483541B2 (en) | 2016-05-09 | 2019-11-19 | Nichia Corporation | Method of producing nickel-cobalt composite hydroxide and method of producing positive electrode active material for non-aqueous electrolyte secondary battery |
CN111167584B (en) * | 2019-12-30 | 2021-08-17 | 贵州武陵锰业有限公司 | Manganese ore industrialization wet ball milling method based on electrolytic manganese anolyte |
Family Cites Families (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3271196A (en) | 1961-11-08 | 1966-09-06 | Leesona Corp | Fuel cell electrodes |
US3508967A (en) | 1967-09-22 | 1970-04-28 | Gulton Ind Inc | Negative lithium electrode and electrochemical battery containing the same |
JPH0789483B2 (en) | 1984-05-07 | 1995-09-27 | 三洋化成工業株式会社 | Secondary battery |
EP0205856B1 (en) | 1985-05-10 | 1991-07-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Secondary battery |
JPH063745B2 (en) | 1986-07-02 | 1994-01-12 | シャープ株式会社 | Non-aqueous electrolyte secondary battery |
US4945014A (en) | 1988-02-10 | 1990-07-31 | Mitsubishi Petrochemical Co., Ltd. | Secondary battery |
GB2221213B (en) * | 1988-07-12 | 1991-09-04 | Csir | Synthesizing lithium manganese oxide |
US5028500A (en) | 1989-05-11 | 1991-07-02 | Moli Energy Limited | Carbonaceous electrodes for lithium cells |
JPH0439859A (en) | 1990-06-04 | 1992-02-10 | Mitsubishi Petrochem Co Ltd | Secondary battery electrode |
US5153082A (en) | 1990-09-04 | 1992-10-06 | Bridgestone Corporation | Nonaqueous electrolyte secondary battery |
JP3133318B2 (en) | 1990-09-18 | 2001-02-05 | 三洋電機株式会社 | Rechargeable battery |
JP3162437B2 (en) | 1990-11-02 | 2001-04-25 | セイコーインスツルメンツ株式会社 | Non-aqueous electrolyte secondary battery |
US5244757A (en) | 1991-01-14 | 1993-09-14 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
DE4101533A1 (en) | 1991-01-19 | 1992-07-23 | Varta Batterie | ELECTROCHEMICAL SECONDARY ELEMENT |
JP3291750B2 (en) | 1992-02-25 | 2002-06-10 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
EP0573266B1 (en) | 1992-06-01 | 1999-12-08 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method of manufacturing carbonaceous material for negative electrode of the battery |
JP2651332B2 (en) * | 1992-09-21 | 1997-09-10 | 松下電工株式会社 | Zirconia-based composite ceramic sintered body and method for producing the same |
EP0601832B1 (en) | 1992-12-07 | 1999-05-19 | Honda Giken Kogyo Kabushiki Kaisha | Alkaline ion-absorbing/desorbing carbon material, electrode material for secondary battery using the carbon material and lithium battery using the electrode material |
JP2699026B2 (en) | 1993-02-18 | 1998-01-19 | エフ エム シー コーポレーション | Alkali metal dispersion |
US5776369A (en) | 1993-02-18 | 1998-07-07 | Fmc Corporation | Alkali metal dispersions |
US5312623A (en) | 1993-06-18 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | High temperature, rechargeable, solid electrolyte electrochemical cell |
JPH0722020A (en) * | 1993-06-29 | 1995-01-24 | Tosoh Corp | Manufacture of lithium-manganese composite oxide and application thereof |
US5370949A (en) | 1993-07-09 | 1994-12-06 | National Research Council Of Canada | Materials for use as cathodes in lithium electrochemical cells |
US5618640A (en) | 1993-10-22 | 1997-04-08 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
CA2127621C (en) | 1994-07-08 | 1999-12-07 | Alfred Macdonald Wilson | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
JPH08213052A (en) | 1994-08-04 | 1996-08-20 | Seiko Instr Inc | Nonaqueous electrolyte secondary battery |
US5543021A (en) | 1994-09-01 | 1996-08-06 | Le Carbone Lorraine | Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator |
FR2724490B1 (en) | 1994-09-09 | 1996-10-25 | Lorraine Carbone | CARBON / POLYMER COMPOSITE ELECTRODE FOR LITHIUM RECHARGEABLE ELECTROCHEMICAL GENERATOR |
US5707756A (en) | 1994-11-29 | 1998-01-13 | Fuji Photo Film Co., Ltd. | Non-aqueous secondary battery |
US5595837A (en) | 1995-04-12 | 1997-01-21 | Valence Technology, Inc. | Process for prelithiation of carbon based anodes for lithium batteries |
US5601796A (en) * | 1995-11-22 | 1997-02-11 | The Board Of Regents Of The University Of Oklahoma | Method of making spinel LI2MN204 compound |
US5753387A (en) | 1995-11-24 | 1998-05-19 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
GB9600772D0 (en) * | 1996-01-15 | 1996-03-20 | Univ St Andrews | Improvements in and relating to electrochemical cells |
US5672446A (en) | 1996-01-29 | 1997-09-30 | Valence Technology, Inc. | Lithium ion electrochemical cell |
US5958622A (en) | 1996-03-28 | 1999-09-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Negative electrode material for lithium secondary batteries |
JPH10117406A (en) | 1996-06-14 | 1998-05-06 | Fuji Photo Film Co Ltd | Electric car and its drive power source unit |
US6270926B1 (en) | 1996-07-16 | 2001-08-07 | Murata Manufacturing Co., Ltd. | Lithium secondary battery |
DE69705428T2 (en) | 1996-12-20 | 2001-10-11 | Danionics As Odense S | LITHIUM SECONDARY BATTERY WITH A NEGATIVE ELECTRODE CONTAINING NATURAL SCALE GRAPHITE |
JPH10223259A (en) | 1997-02-03 | 1998-08-21 | Toyota Central Res & Dev Lab Inc | Lithium secondary battery and manufacture thereof |
JP3613400B2 (en) | 1997-02-28 | 2005-01-26 | 旭化成エレクトロニクス株式会社 | Non-aqueous secondary battery and manufacturing method thereof |
US6156457A (en) | 1997-03-11 | 2000-12-05 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method for manufacturing a negative electrode |
JP3036694B2 (en) | 1997-03-25 | 2000-04-24 | 三菱重工業株式会社 | Method for producing Li composite oxide for Li-ion battery electrode material |
JP3200025B2 (en) | 1997-03-26 | 2001-08-20 | セイコーインスツルメンツ株式会社 | Non-aqueous electrolyte secondary battery |
US5807645A (en) | 1997-06-18 | 1998-09-15 | Wilson Greatbatch Ltd. | Discharge promoter mixture for reducing cell swelling in alkali metal electrochemical cells |
JPH1125975A (en) | 1997-07-02 | 1999-01-29 | Toyota Central Res & Dev Lab Inc | Negative electrode active material |
US5948569A (en) | 1997-07-21 | 1999-09-07 | Duracell Inc. | Lithium ion electrochemical cell |
KR100245808B1 (en) | 1997-12-30 | 2000-03-02 | 박찬구 | Process for manufacturing lithium ion secondary battery electrode compounds |
FR2777387B1 (en) * | 1998-04-14 | 2000-05-12 | Commissariat Energie Atomique | LITHIUM BATTERY OPERATING BETWEEN 1.8 VOLTS AND 4.3 VOLTS |
FR2777388B1 (en) * | 1998-04-14 | 2000-05-12 | Commissariat Energie Atomique | LITHIUM ACCUMULATOR OPERATING UP TO A HIGH VOLTAGE TERMINAL OF 3.5 VOLTS |
AU3978599A (en) * | 1998-05-11 | 1999-11-29 | Duracell Inc. | Lithiated manganese oxide |
US6190800B1 (en) * | 1998-05-11 | 2001-02-20 | The Gillette Company | Lithiated manganese dioxide |
US6168885B1 (en) | 1998-08-21 | 2001-01-02 | Sri International | Fabrication of electrodes and devices containing electrodes |
JP2000067853A (en) | 1998-08-18 | 2000-03-03 | Matsushita Battery Industrial Co Ltd | Negative electrode for lithium secondary battery |
DE19839217C2 (en) | 1998-08-28 | 2001-02-08 | Fraunhofer Ges Forschung | Pasty masses, layers and layer structures, cells and processes for their production |
GB9819696D0 (en) * | 1998-09-11 | 1998-11-04 | Aea Technology Plc | Manganese oxide-based material |
US6267943B1 (en) | 1998-10-15 | 2001-07-31 | Fmc Corporation | Lithium manganese oxide spinel compound and method of preparing same |
JP2000164210A (en) | 1998-11-24 | 2000-06-16 | Fuji Photo Film Co Ltd | Non-aqueous secondary battery |
KR100326457B1 (en) | 1999-03-10 | 2002-02-28 | 김순택 | A positive active material for a lithium secondary battery and a method of preparing the same |
SE516891C2 (en) | 1999-06-14 | 2002-03-19 | Ericsson Telefon Ab L M | Binder and / or electrolyte material for an electrode in a battery cell, electrode for a battery cell, and process for producing a binder and / or electrolyte material for an electrode |
US6541156B1 (en) | 1999-11-16 | 2003-04-01 | Mitsubishi Chemical Corporation | Negative electrode material for non-aqueous lithium secondary battery, method for manufacturing the same, and non-aqueous lithium secondary battery using the same |
US6403257B1 (en) | 2000-07-10 | 2002-06-11 | The Gillette Company | Mechanochemical synthesis of lithiated manganese dioxide |
EP1180810A2 (en) * | 2000-08-18 | 2002-02-20 | Nissan Motor Co., Ltd. | Positive electrode active material for rechargeable lithium-ion battery |
JP2002124258A (en) * | 2000-10-13 | 2002-04-26 | Toda Kogyo Corp | Lithium manganate particle powder and its manufacturing method |
US6706447B2 (en) * | 2000-12-22 | 2004-03-16 | Fmc Corporation, Lithium Division | Lithium metal dispersion in secondary battery anodes |
US7276314B2 (en) | 2000-12-22 | 2007-10-02 | Fmc Corporation | Lithium metal dispersion in secondary battery anodes |
US8980477B2 (en) | 2000-12-22 | 2015-03-17 | Fmc Corporation | Lithium metal dispersion in secondary battery anodes |
JP2004006423A (en) * | 2001-04-10 | 2004-01-08 | Mitsui Mining & Smelting Co Ltd | Active material for lithium secondary battery |
JP4310937B2 (en) * | 2001-06-18 | 2009-08-12 | 新神戸電機株式会社 | Lithium secondary battery |
JP2003007297A (en) * | 2001-06-20 | 2003-01-10 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery |
JP2003168431A (en) * | 2001-11-30 | 2003-06-13 | Toyota Central Res & Dev Lab Inc | Positive electrode active material for lithium secondary battery, its manufacturing method and lithium secondary battery using the same |
DK200200615A (en) | 2001-12-19 | 2003-06-20 | Fmc Corp | Lithium metal dispersion in secondary battery nodes |
US20050130043A1 (en) | 2003-07-29 | 2005-06-16 | Yuan Gao | Lithium metal dispersion in electrodes |
JP4126374B2 (en) | 2003-10-22 | 2008-07-30 | 独立行政法人産業技術総合研究所 | Composition for producing biological models such as blood vessel walls and internal organs |
US7771874B2 (en) * | 2005-06-29 | 2010-08-10 | Fmc Corporation | Lithium manganese compounds and methods of making the same |
-
2006
- 2006-06-28 US US11/477,070 patent/US7771874B2/en active Active
- 2006-06-29 CN CN2006800238545A patent/CN101213146B/en active Active
- 2006-06-29 CA CA2610077A patent/CA2610077C/en not_active Expired - Fee Related
- 2006-06-29 DE DE112006001610.5T patent/DE112006001610B4/en active Active
- 2006-06-29 GB GB0721258A patent/GB2439890B/en active Active
- 2006-06-29 KR KR1020077030597A patent/KR101368855B1/en active IP Right Grant
- 2006-06-29 EP EP06786033.8A patent/EP1896366B1/en active Active
- 2006-06-29 JP JP2008519633A patent/JP5096329B2/en not_active Expired - Fee Related
- 2006-06-29 RU RU2007149066/15A patent/RU2007149066A/en not_active Application Discontinuation
- 2006-06-29 WO PCT/US2006/025694 patent/WO2007002907A2/en active Application Filing
- 2006-06-29 CA CA2840566A patent/CA2840566C/en not_active Expired - Fee Related
- 2006-06-29 KR KR1020137004550A patent/KR101389409B1/en active IP Right Grant
-
2010
- 2010-07-07 US US12/831,420 patent/US20100270498A1/en not_active Abandoned
-
2013
- 2013-11-21 US US14/086,289 patent/US9896345B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
DE112006001610B4 (en) | 2023-09-14 |
US9896345B2 (en) | 2018-02-20 |
CA2840566C (en) | 2016-12-06 |
GB2439890B (en) | 2011-06-08 |
CN101213146B (en) | 2012-07-18 |
RU2007149066A (en) | 2009-07-10 |
GB0721258D0 (en) | 2007-12-05 |
EP1896366A2 (en) | 2008-03-12 |
WO2007002907A2 (en) | 2007-01-04 |
CA2610077C (en) | 2014-04-08 |
WO2007002907A3 (en) | 2007-05-18 |
CA2840566A1 (en) | 2007-01-04 |
DE112006001610T5 (en) | 2008-05-29 |
KR101389409B1 (en) | 2014-04-25 |
US20100270498A1 (en) | 2010-10-28 |
JP2009500277A (en) | 2009-01-08 |
US20140077127A1 (en) | 2014-03-20 |
CN101213146A (en) | 2008-07-02 |
KR20080021710A (en) | 2008-03-07 |
EP1896366B1 (en) | 2018-01-10 |
JP5096329B2 (en) | 2012-12-12 |
US20070003834A1 (en) | 2007-01-04 |
US7771874B2 (en) | 2010-08-10 |
KR101368855B1 (en) | 2014-03-17 |
GB2439890A (en) | 2008-01-09 |
KR20130033458A (en) | 2013-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2610077C (en) | Lithium manganese compounds and methods of making the same | |
JP4326041B2 (en) | Doped intercalation compound and method for producing the same | |
KR102307224B1 (en) | Compositions containing doped nickelate compounds | |
JP7236459B2 (en) | O3/P2 Mixed Phase Sodium Containing Doped Layered Oxide Materials | |
JP3670875B2 (en) | Lithium secondary battery | |
WO2005028371A1 (en) | Composite oxide containing lithium, nickel, cobalt, manganese, and fluorine, process for producing the same, and lithium secondary cell employing it | |
Jeong et al. | Electrochemical studies on cathode blends of LiMn2O4 and Li [Li1/15Ni1/5Co2/5Mn1/3O2] | |
JP2003002661A (en) | Method for producing lithium cobalt composite oxide | |
WO2018096999A1 (en) | Lithium-manganese complex oxide and method for producing same | |
JP4189457B2 (en) | Lithium ion secondary battery | |
JP2000154022A (en) | Lithium manganese double oxide, its production and its use | |
JP2002298843A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery, and method for manufacturing the same | |
JP2000154021A (en) | New lithium manganese oxide, its production and its use | |
Radzi et al. | Layered and spinel structures as lithium-intercalated compounds for cathode materials | |
WO2022034329A1 (en) | Process for preparing lithium nickel composite oxide, lithium nickel composite oxide, electrode material comprising it and method to prepare it | |
AU2021326031A1 (en) | Cathode materials | |
JP2003007297A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery | |
NAKANO et al. | Hydrothermal synthesis of lithium manganese oxide with α-NaFeO2 structure | |
JP2002056850A (en) | DIFFERENT KIND ELEMENT SUBSTITUENT Li-Mn SPINEL AND METHOD OF BURNING THE SAME |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20210629 |