CN103138002B - Lithium-sulfur cell and preparation method thereof - Google Patents

Lithium-sulfur cell and preparation method thereof Download PDF

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CN103138002B
CN103138002B CN201310071234.0A CN201310071234A CN103138002B CN 103138002 B CN103138002 B CN 103138002B CN 201310071234 A CN201310071234 A CN 201310071234A CN 103138002 B CN103138002 B CN 103138002B
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lithium
electrolyte
positive pole
sulphur
sulfur cell
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CN103138002A (en
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吴晓东
胡园园
许晶晶
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • 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

The invention discloses a kind of lithium-sulfur cell and preparation method thereof.This lithium-sulfur cell comprises positive pole, electrolyte and contains cathode of lithium, and described electrolyte comprises solvent and electrolyte, and wherein, described positive pole preferably adopts the porous electrode of not sulfur-bearing, and also containing sulphur and/or sulfide in described electrolyte, described electrolyte comprises lithium salts; Its preparation method comprises: prepare positive pole, electrolyte respectively and contain cathode of lithium, and this three is assembled formation target product.The invention provides a kind of simple lithium-sulfur cell system, avoid the complicated preparation process of sulphur positive pole, decrease process costs, and the skewness of active material sulphur in traditional sulphur positive electrode or the oversize capacity caused can be avoided to be difficult to play, the problems such as the utilance of sulphur is low, and battery performance is unstable.

Description

Lithium-sulfur cell and preparation method thereof
Technical field
The present invention relates to a kind of lithium battery, particularly a kind of lithium-sulfur cell and preparation method thereof.
Technical background
Lithium-sulfur cell is with the attention of cheap, superiority the receives research staff such as memory space is large of its incomparable height ratio capacity and energy density and material, especially in recent years the domestic and international research to lithium-sulfur cell was quite active, and technological break-through has reached the stage of practical application.Traditional Li/S battery is all that active material sulphur or sulfide are fixed on positive pole, supposes that the sulphur complete reaction of positive pole generates Li 2s, the theoretical specific capacity that then can discharge is 1672mAh/g, theoretical specific energy is 2600Wh/Kg, the performance of an order of magnitude has been exceeded than positive electrodes such as metal oxides commercial at present, be rated as most potential lithium ion battery of new generation, for electric automobile, the contour energy dissipation device of hybrid electric vehicle, space flight and aviation provides energy, simultaneously again can as the energy-storage battery of Cheap highly effective.At scientific research field, main power all concentrates on research positive pole, prepare diversified sulfur-bearing positive electrode, as the sulphur of synthesis of nano size, synthesis carbon-sulfur compound and sulfur-bearing conducting polymer etc. improve the utilance of sulphur, suppress intermediate product to gather sulfide and be dissolved in electrolyte, improve efficiency for charge-discharge.In battery industry, some enterprises have developed the lithium-sulfur cell of high-energy-density and have been put to production application both at home and abroad.Recently call in the world and only can not be confined to positive and negative pole material to the work of lithium-sulfur cell improvement in performance, also the innovation on the design structure of whole battery system should be focused on, as designed battery structure with conductive carbon film as the method for intercalation, improve lithium-sulfur cell cycle performance, improve efficiency for charge-discharge.Then, making a general survey of aforesaid technology is all around synthesis sulfur-bearing anode composite, by the synthetic method of complexity, expensive raw material and high-end technology to obtaining good performance, but due to loss, cycle performance or the Shortcomings of active material cannot be avoided completely.
Summary of the invention
For the deficiencies in the prior art, main purpose of the present invention is to provide a kind of lithium-sulfur cell, its have simplify the structure, the feature such as low cost, simple process, also there is good capacity simultaneously and play performance.
Another object of the present invention is to provide a kind of method preparing aforementioned lithium-sulfur cell.
For realizing above-mentioned technical purpose, present invention employs following technical scheme:
A kind of lithium-sulfur cell, comprise positive pole, electrolyte and contain cathode of lithium, described electrolyte comprises solvent and electrolyte, and wherein, also containing sulphur and/or sulfide in described electrolyte, described electrolyte comprises lithium salts.
Further, describedly comprise lithium metal or lithium alloy containing cathode of lithium, described lithium alloy comprises any one or two or more combinations in lithium and H, Na, K, Be, Mg, Ca, Ag, B, Al, Ga, In, C, Si, Ge, Sn, Zn, Pb, N, P, Sb, Bi, Se and Te.
In described electrolyte, the concentration of contained element sulphur is preferably 0.05-10mol/L.
In described electrolyte, the total concentration of contained lithium salts is preferably 0.5-10mol/L.
As one of comparatively preferred embodiment, also protect additive containing in order to protection containing the negative pole of cathode of lithium in described electrolyte, described negative pole protection additive can be selected from but be not limited to nitrate, alkoxy silane etc.
Described solvent comprises at least in order to dissolve the first solvent of lithium salts and the second solvent in order to promote elemental sulfur and/or sulphide dissolves degree, described first solvent comprises ether solvent, described ether solvent can be selected from but be not limited to 1,3-dioxolanes or diethylene glycol dimethyl ether etc., described second solvent can be selected but be not limited to carbon disulfide, benzene or derivatives thereof, toluene and oxolane or derivatives thereof etc.
As one of comparatively preferred embodiment, in described solvent, the cumulative volume of the first solvent is 0.95 ~ 0.50:1 with the ratio of the cumulative volume of the second solvent.
As one of comparatively preferred embodiment, described positive pole comprises porous electrode, and described porous electrode comprises collector and is coated in the conductive powder being mixed with binding agent on described collector;
Or described porous electrode comprises the porous, electrically conductive structure formed by electro-deposition or micro-processing method.
As one of comparatively preferred embodiment, the described lithium negative electrode that contains comprises lithium or lithium alloy electrode.
As one of comparatively preferred embodiment, the preparation method of this lithium-sulfur cell can comprise:
(1) provide positive pole, comprising:
A. get porous conductive material, binding agent and solvent and form anode sizing agent, and coating on a current collector, forms positive pole after drying; Or,
B. power taking deposition or chemical deposition solution form alloy-layer at deposited on substrates, and more than one selected alloying component and/or substrate material in then etching removing alloy-layer, form the positive pole with loose structure;
(2) provide containing cathode of lithium, comprising:
A. power taking deposit solution deposits and forms lithium or lithium alloys boundary layer in conductive current collector; Or,
B. direct lithium or lithium alloys are cut into required shape and with battery lead electrode phase compound;
(3) provide electrolyte, comprising:
I. get sublimed sulfur simple substance and be dissolved in carbon disulfide, and dissolve saturated;
II. getting negative pole protection additive, to be dissolved in primarily of volume ratio be in the mixed solvent that formed of 1, the 3-dioxolanes of 1:1 and diethylene glycol dimethyl ether, and the lithium salts containing 1M in described mixed solvent;
III. get step I obtain mixture and step II obtain mixture and mix according to the volume ratio of 2:8-3:7, obtain electrolyte for subsequent use;
(4) get described positive pole, form lithium-sulfur cell containing cathode of lithium and electrolyte combination.
Compared with prior art, advantage of the present invention is at least: by by active material sulphur or sulphide dissolves in electrolyte, and make positive pole just serve as conductive electrode, eliminate the complicated preparation process of traditional sulphur positive electrode, simple for process, low for equipment requirements, with low cost, and the problems such as the skewness of active material sulphur in traditional sulphur positive electrode or the oversize capacity caused are difficult to play, and the utilance of sulphur is low, and battery performance is unstable can be avoided.
Embodiment
As previously mentioned, in view of the deficiencies in the prior art, one aspect of the present invention aims to provide a kind of lithium-sulfur cell, and it is different from the structure that conventional lithium-sulfur cell adopts sulphur positive pole, but is dissolved in electrolyte by active material sulphur.
Further say, the formation of this lithium-sulfur cell mainly has lithium metal or lithium alloy is negative pole, and the electrode of conductive porous structure is as positive pole and have the electrolyte dissolving lithium salts and active material sulphur simple substance or sulfide.
Obviously can see, the present invention is to provide a kind of simple lithium-sulfur cell system, it can avoid the complicated preparation process of traditional sulphur positive pole, decreases process costs.
As preferably one of embodiment, aforementioned positive electrode preferably adopts the porous electrode of conduction, porous electrode can be conductive powder coating formed on a current collector, also can be the loose structure etc. formed by electro-deposition or micro-machined method, conductive electrode can be conventional carbonaceous conductive matter (as: conductive black, carbon pipe, acetylene black etc.) or torpescence metal etc.
Obvious, aforementioned positive electrode can adopt the electrode of sulfur-bearing or not sulfur-bearing, preferably adopts the electrode of not sulfur-bearing.
Aforementioned negative pole can be lithium metal, can be also lithium alloy, containing one or more in following metal in lithium alloy: H, Na, K, Be, Mg, Ca, Ag, B, Al, Ga, In, C, Si, Ge, Sn, Zn, Pb, N, P, Sb, Bi, Se, Te.
As preferably one of embodiment, the active material be dissolved in aforementioned electrolyte can be sulphur also can be sulfide, in aforementioned electrolyte, also there are more than one lithium salts simultaneously, as conventional two (trifluoromethane sulfonic acid acyl) imine lithium (LiTFSI), lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiCl 4) etc., ensure electrolyte have general lithium ion battery conductivity require (be more than or equal to 10 -3s/cm).
Preferably, in aforementioned electrolyte, the concentration of lithium salts is 0.5-10mol/L.
Further; the additive can protecting lithium anode also can be added in aforementioned electrolyte; as lithium nitrate; dimethyldimethoxysil,ne; tetramethoxy-silicane etc.; to form solid electrolyte interface diaphragm on negative pole lithium surface, stop the active material and cathode of lithium generation side reaction that are dissolved in electrolyte.
The solvent of aforementioned electrolyte mainly adopts 1,3-dioxolanes (DOL), the ether solvents such as diethylene glycol dimethyl ether (DME), its solubilized lithium salts.
Meanwhile, also should comprise in electrolyte can the solvent of larger dissolving sublimed sulfur or sulfide, and as carbon disulfide etc., and in order to the high conductivity ensureing electrolyte, low viscous feature, the mass fraction of carbon disulfide preferably controls between 5-60%.
Postscript, the concentration being dissolved in the sulphur in electrolyte preferably controls at 0.05-10mol/L.
Such as, in one preferably embody rule scheme, be dissolved in sulphur in aforementioned electrolyte or sulfide concentration can be 0.1-3mol/L, charge and discharge potential is between 1.0-3.0V.
As preferably one of embody rule scheme, the DOL:DME:CS that volume ratio is more than or equal to 1:1:1 in aforementioned solvents, can be comprised 2.
As preferably one of embody rule scheme, the preparation method of aforementioned lithium-sulfur cell can comprise the following steps:
1. the preparation method of positive pole:
(1) cladding process prepares porous electrode
A, selection porous conductive material, as micro-, mesoporous activated carbon, nickel foam particle etc.;
B, porous material and binding agent to be dissolved in solvent uniformly by proper proportion;
C, the anode sizing agent of b is coated on plus plate current-collecting body;
D, vacuum drying solvent, store for future use.
(2) electrodeposition process prepares porous electrode
A, surface treatment and cleaning are carried out to the substrate of porous anode;
The electric depositing solution of b, preparation porous electrode material;
C, in electrode substrate deposit alloy (as metal alloys such as Pt, Ni, Cu)
D, the method removing that one or more components utilisings in the alloy be deposited on substrate are etched.
E, to formed porous electrode again clean removing surface impurity, dry after for subsequent use.
2. the preparation method of negative pole, comprising:
A. power taking deposit solution deposits and forms lithium or lithium alloys boundary layer in conductive current collector; Or,
B. direct lithium or lithium alloys are cut into required shape and with battery lead electrode phase compound;
Further, also can form boundary layer protection negative pole at aforementioned lithium or lithium alloys surface, the material of the material of this boundary layer mainly lithium ion conduct electrons insulation, as: oxide, phosphate, fluoride etc.
It should be noted that, the lithium of negative pole or lithium alloy can be sheet also can be other patterns.
3. the preparation method of electrolyte:
A, by appropriate sulphur simple substance or sulphide dissolves in a solvent, ensureing that under the high conductivity of electrolyte, low viscous prerequisite, active material sulphur concentration is in the electrolytic solution the bigger the better.
B, be dissolved in solvent by the negative pole of the lithium salts of 0.5-1.5mol/L and 0.1-0.3mol/L protection additive, solvent here can one or more mixed solvents, as DOL, DME or other straight chain, cyclic ether kind solvent.
C, slowly drip in b electrolyte by the solution in a, both guarantees are dissolved completely.
The volume ratio of d, control a and b solution is between 2:8 to 3:7.
E, the sulfur-bearing electrolyte prepared is positioned in hothouse or glove box stores.
Below in conjunction with some preferred embodiments, technical scheme of the present invention is further described.
Embodiment 1: positive pole adopts conduction nickel screen, and negative pole adopts metal lithium sheet, and 2mol/L sublimed sulfur is dissolved in 30mL electrolyte that (solvent is DOL:DME:CS by volume 2=2:2:1, lithium salt is the LiNO of LiTFSI and 0.2mol/L of 1.0mol/L 3), equip the self-control battery testing performance of two electrodes, the size of current of test is 0.5mA, and discharge and recharge scope is at 1.5-3.0V.
Embodiment 2: positive pole adopts conductive foam nickel, and other steps are as embodiment 1.
Embodiment 3: positive pole adopts conductive foam nickel, and the size of current of test is 0.6,0.7,0.8,0.9,1.0mA, and other steps are as embodiment 1.
Embodiment 4: change solvent C S2 volume accounting example 10%, 20%, 30% in the electrolytic solution, other steps are as embodiment 1.
Embodiment 5: the concentration of active material sulphur is respectively 0.2,0.5,1.0,1.5,2.0mol/L, other steps are as embodiment.
Embodiment 6: positive pole adopts aluminium foil, other steps can refer to embodiment 1-5 and implement.
It may be noted that and be, for the person of ordinary skill of the art, other various corresponding change and distortion can be made according to technical solution of the present invention and technical conceive, and these change and be out of shape the protection range that all should belong to the claims in the present invention.

Claims (1)

1. a preparation method for lithium-sulfur cell, is characterized in that, comprising:
(1) provide positive pole, comprising:
A. get porous conductive material, binding agent and solvent and form anode sizing agent, and coating on a current collector, forms positive pole after drying; Or,
B. power taking deposition or chemical deposition solution form alloy-layer at deposited on substrates, and more than one selected alloying component and/or substrate material in then etching removing alloy-layer, form the positive pole with loose structure;
(2) provide containing cathode of lithium, comprising:
A. power taking deposit solution deposits and forms lithium or lithium alloys boundary layer in conductive current collector; Or,
B. direct lithium or lithium alloys are cut into required shape and with battery lead electrode phase compound;
(3) provide electrolyte, comprising:
I. get sublimed sulfur simple substance and be dissolved in carbon disulfide, and dissolve saturated;
II. getting negative pole protection additive, to be dissolved in primarily of volume ratio be in the mixed solvent that formed of 1, the 3-dioxolanes of 1:1 and diethylene glycol dimethyl ether, and the lithium salts containing 1M in described mixed solvent;
III. get step I obtain mixture and step II obtain mixture and mix according to the volume ratio of 2:8-3:7, obtain electrolyte for subsequent use;
(4) get described positive pole, form lithium-sulfur cell containing cathode of lithium and electrolyte combination.
CN201310071234.0A 2013-03-06 2013-03-06 Lithium-sulfur cell and preparation method thereof Active CN103138002B (en)

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Publication number Priority date Publication date Assignee Title
CN106340663B (en) * 2015-07-06 2019-04-09 中国科学院大连化学物理研究所 A kind of list liquid stream lithium-sulfur cell
CN105680040B (en) * 2016-01-12 2019-03-29 浙江大学 A kind of antimony base lithium storage materials and preparation method thereof
CN107623143B (en) * 2016-07-14 2020-04-17 中国科学院上海硅酸盐研究所 Lithium-sulfur battery electrolyte containing functional additive and application thereof
CN106785049A (en) * 2016-12-21 2017-05-31 厦门大学 A kind of lithium-sulfur cell electrolyte and its application
CN108899500A (en) * 2018-06-28 2018-11-27 肇庆市华师大光电产业研究院 A kind of preparation method of lithium sulfur battery anode material
CN109786829B (en) * 2018-12-14 2020-06-30 深圳启辰新能源科技有限公司 Lithium-sulfur battery electrolyte and preparation method thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
US5582623A (en) * 1994-11-23 1996-12-10 Polyplus Battery Company, Inc. Methods of fabricating rechargeable positive electrodes
CN1423843A (en) * 2000-02-01 2003-06-11 波利普拉斯电池有限公司 Liquid electrolyte lithium-sulfur batteries

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US5582623A (en) * 1994-11-23 1996-12-10 Polyplus Battery Company, Inc. Methods of fabricating rechargeable positive electrodes
CN1423843A (en) * 2000-02-01 2003-06-11 波利普拉斯电池有限公司 Liquid electrolyte lithium-sulfur batteries

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