CN102185127A - Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery - Google Patents

Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery Download PDF

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Publication number
CN102185127A
CN102185127A CN2011100862086A CN201110086208A CN102185127A CN 102185127 A CN102185127 A CN 102185127A CN 2011100862086 A CN2011100862086 A CN 2011100862086A CN 201110086208 A CN201110086208 A CN 201110086208A CN 102185127 A CN102185127 A CN 102185127A
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lithium
carbon
sulfur cell
adsorbent
characterized
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CN2011100862086A
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Chinese (zh)
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木士春
陈伟
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武汉理工大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

The invention relates to a lithium sulphur battery anode piece added with an absorbent and a lithium sulphur battery. In the invention, a material which has the characteristics of high specific surface area and strong absorption performance is used as the absorbent; the absorbent is added into the anode piece of the lithium sulphur battery; and the addition amount of the absorbent is more than 5% of the mass of the anode piece. The added absorbent can absorb the polysulfide of the lithium sulphur battery in the charge and discharge courses, thereby avoiding the polysulfide from being absorbed on the surface of a sulfhydryl composite material to reduce the electrical conductivity, and can simultaneously prevent the polysulfide from being scattered on the surface of the cathode and generating a corrosion reaction with lithium to further cause the irreversible capacity loss of the battery. Thus, the added absorbent can be used for improving the performance of the lithium sulphur battery provided by the invention.

Description

A kind of positive pole plate of lithium-sulfur cell and lithium-sulfur cell that adds adsorbent

Technical field

The present invention relates to the lithium-sulfur cell technical field, particularly a kind of positive pole plate of lithium-sulfur cell and lithium-sulfur cell that adds adsorbent.

Technical background

Positive electrode is the bottleneck of restriction lithium battery development always, and present business-like lithium battery active material mainly is LiCoO 2, LiMnO 4Deng.The phase anticathode, business-like positive electrode specific capacity is too low, LiCoO 2Specific capacity be 130~140mAh/g, LiMnO 4Specific capacity be 110~130mAh/g, and they cost an arm and a leg.Therefore develop novel green energy storage positive electrode and just seem particularly crucial and urgent with high-energy-density, low cost and long circulation life.

Elemental sulfur has advantages such as height ratio capacity, cheap, hypotoxicity as positive electrode.The theoretical specific capacity of elemental sulfur is 1675mAh/g, and theoretical specific energy is 2600Wh/Kg, is that specific capacity is the highest in the positive electrode of being understood at present, is far longer than business-like secondary cell of present stage.Moreover, the operating voltage of lithium-sulfur cell can satisfy the application demand of present multiple occasion about 2.1V, and the low price of elemental sulfur, source are abundant, and therefore the research and development around lithium-sulfur cell and critical material thereof receive much concern.Though lithium-sulfur cell uses elemental sulfur to have lot of advantages such as specific capacity height, cost are low as positive electrode, but problem such as also exist poor electric conductivity, capacity attenuation is fast and cycle life is short, in addition, also exist because of many lithium sulfides and in electrolyte, dissolve " the flying the shuttle phenomenon " that causes.

Studies show that the main cause of lithium-sulfur cell capacity attenuation is the destruction of electrode structure pattern.In the process of discharge, elemental sulfur at first is reduced and generates the solubility polysulfide, the intermediate product polysulfide of discharge process dissolves in electrolyte easily, cause the enclosed pasture efficient of battery charging and discharging to reduce, and its can along with electrolyte be diffused into negative terminal surface and with lithium generation corrosion reaction, cause irreversible capacitance loss.Along with the carrying out of discharge process, the solubility polysulfide finally is reduced into Li 2S and Li 2S 2Discharge end product Li in the positive electrode 2S and Li 2S 2The conductivity extreme difference, its can cover the surface of positive electrode active materials with the form of solid film, thereby hinders the electrochemical reaction between electrolyte and electrode active material.Therefore, how solving the problems of dissolution of charge and discharge process intermediate product, improve the cycle performance of battery, is one of the emphasis that will study of sulfenyl positive electrode.

In order to improve the cycle performance of lithium-sulfur cell, the present invention inserts adsorbent in existing positive electrode, the polysulfide that produces in charge and discharge process in order to the absorption lithium-sulfur cell also suppresses the generation of " flying the shuttle phenomenon ", to improve the performance and the useful life of lithium-sulfur cell.

Summary of the invention

The purpose of this invention is to provide a kind of lithium-sulfur cell that adds the positive pole plate of lithium-sulfur cell of adsorbent and contain anode pole piece of the present invention.

Traditional positive pole plate of lithium-sulfur cell mainly is made up of positive electrode active materials, binding agent and conductive agent.In order to improve the easily dissolving and be diffused into negative pole with electrolyte and cause problems such as battery capacity decay, cycle performance reduction in electrolyte of lithium-sulfur cell intermediate product polysulfide, the present invention has added adsorbent in positive pole plate of lithium-sulfur cell, the adsorbent addition is more than 5% of anode pole piece quality.

The quality percentage composition of anode pole piece of the present invention is: positive electrode active materials 50%~75%, and conductive agent 10%~20%, binding agent 10%~20%, adsorbent are 5%~15%.

Adsorbent of the present invention is dispersed among the anode pole piece material.

In the anode pole piece of the present invention, adsorbent is mainly selected the material that has high-specific surface area, loose structure and have good adsorption properties for use, as active carbon, carbosphere, mesoporous carbon, carbon molecular sieve, carbide derived carbon (pore-size distribution 0.5~5nm) and polymeric adsorbent etc.Sorbing material depends primarily on Surface Physical and chemical constitution to the absorption of adsorption molecule.Sorbing material also is divided into two kinds of physical absorption and chemisorbed to the absorption of adsorbate.Physical absorption is owing to Van der Waals force causes, chemisorbed then is that the chemical bond power effect between adsorbent surface and the adsorbate causes that most of adsorption processes are physical absorption.

Van der Waals force has the sorbing material of loose structure and high surface owing to can form powerful absorption field at material surface, after adsorbate is adsorbed in the aperture structure of sorbing material, the capillary adsorption in aperture can reinforcing material to the absorption of adsorbate.

The used positive electrode active materials of lithium-sulfur cell is generally carbon sulphur composite material or metal sulfide material, and carbon is carbon nano-tube, mesoporous carbon, active carbon and carbide derived carbon etc. in the carbon sulphur composite material, and the metal sulfide material is MoS 2, FeS 2, V 2S 2Or NiS.Positive electrode active materials can produce the transiting product polysulfide in the process of battery charging and discharging.Polysulfide is easily dissolving in electrolyte, and along with electrolyte migrates to negative pole, reacts with negative pole and corrodes negative pole, causes the performance of battery to reduce.So, add sorbing material in the lithium-sulfur cell kind and can not only effectively adsorb the polysulfide that is dissolved in the electrolyte, stop its migration in lithium-sulfur cell, and can prevent the end product Li that discharges 2S 2And Li 2S covers surface of positive electrode active material, thereby improves the performance and the cycle life of lithium-sulfur cell.

The present invention adds sorbing materials such as active carbon, carbosphere, mesoporous carbon, carbide derived carbon or polymeric adsorbent, in order to improve the lithium-sulfur cell performance in cell positive material when preparation anode pole piece.The anode pole piece of the present invention's preparation is assembled into lithium-sulfur cell, detects its chemical property, concrete preparation process is as follows:

1. the preparation of positive electrode: take by weighing the needed various materials of preparation anode pole piece, comprise: positive electrode active materials, conductive agent, binding agent and adsorbent, by mass percentage, positive electrode active materials 50%~75%, conductive agent 10%~20%, binding agent 10%~20%, adsorbent are 5%~15%.Positive electrode active materials is carbon sulphur composite material or metal sulfide material.Carbon sulphur composite material is active carbon and sulphur composite material, carbon nano-tube and composite material, mesoporous carbon and sulphur composite material, and carbide derived carbon and sulphur composite material; The metal sulfide material is MoS 2, FeS 2, V 2S 2Or NiS.Binding agent is the Kynoar solution of 15wt%, and solvent is the N-methyl pyrrolidone in its solution.Conductive agent is selected acetylene black or superconduction carbon black.Each anode constituents material is fully disperseed with absolute ethyl alcohol and grinds evenly to obtain anodal slip, the anodal slip that makes is coated in makes sheet on the nickel foam, dry anode pole piece.

2. cell preparation: prepared anode pole piece is assembled lithium-sulfur cell with negative pole and barrier film, anodally uses aluminium flake to be collector, negative pole use copper sheet is made collector.Negative pole is selected metal lithium sheet or lithium alloy for use, and lithium alloy is Li and Si alloy, Li and Sn alloy or Li and C alloy etc.Barrier film is selected polypropylene, polyethylene, Kynoar or polypropylene and polyethylene duplicature for use.Electrolyte is liquid, solid-state or gel-like electrolyte, liquid electrolyte is mainly selected some linear ethers or carbonates solvent for use, as ethylene carbonate methyl esters, propene carbonate, dimethyl carbonate, dioxolanes, tetraethyleneglycol dimethyl ether or oxolane etc., commonly used is two or more mixed organic solvents, as ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate mixed solvent, butyl oxide link and tetraethyleneglycol dimethyl ether mixed solvent.The support solute is lithium hexafluoro phosphate, lithium perchlorate or trifluoromethyl sulfonic acid lithium etc.

The test lithium-sulfur cell is unified to be CR2025 type button cell, and the battery charging and discharging test condition is: under the room temperature environment, and at deboost 1.2~3.0V, charging and discharging currents density 0.15mA/cm 2Condition under carry out charge-discharge test.

Description of drawings

Fig. 1 is the lithium-sulphur cell positive electrode schematic diagram that does not add adsorbent.

Fig. 2 is that adsorbent disperses to add to the lithium-sulphur cell positive electrode schematic diagram in the anode pole piece.

The interpolation that Fig. 3 embodiment 1 and Comparative Examples 1 obtain adsorbent lithium-sulfur cell with do not add the lithium-sulfur cell cycle performance correlation curve of adsorbent.

Among the figure: 1-collector, 2-barrier film, 3-binding agent, 4-conductive agent, 5-active material, 6-adsorbent.

Embodiment

Further specify the preparation of positive pole plate of lithium-sulfur cell of the present invention and contain the lithium-sulfur cell of anode pole piece of the present invention below by embodiment.

Positive pole plate of lithium-sulfur cell quality of the present invention percentage composition is: positive electrode active materials 50%~75%, and conductive agent 10%~20%, binding agent 10%~20%, adsorbent are 5%~15%.

Embodiment 1

Selecting specific area for use is 1000m 2The active carbon of/g is made adsorbent, adsorbent shared mass percent in positive electrode is 15%, positive electrode active materials is carbon nano-tube and sulphur composite material, acetylene black is made conductive agent, the PVDF of 5wt% (Kynoar) solution (solvent is NMP, the N-methyl pyrrolidone) is as the anodal slip of adhesive preparation; Then slip is coated in and is prepared into anode pole piece on the nickel foam, oven dry promptly obtains required anode pole piece, and the thickness of anode pole piece is 45~55um.Select for use the Celgard2400 film to be assembled into battery as battery diaphragm, electrolyte is the LiPF6/EC of 1mol/L: DMC: EMC (1: 1: 1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate, EMC: methyl ethyl carbonate), the entire cell assembling process is all finished in glove box.

The constant current charge-discharge test result shows that the first discharge specific capacity of this battery reaches 945.8mAh/g, after 50 charge and discharge cycles, still remains on 549.2mAh/g, the results are shown in shown in Figure 3.Compare with the battery that does not add adsorbent, the battery that has added adsorbent has demonstrated good battery performance.

Embodiment 2

Select for use active carbon and sulphur composite material as positive electrode active materials, porous carbon microsphere prepares anode pole piece as sorbent material, wherein conductive agent is the superconduction carbon BP 2000, and the mass ratio of positive electrode active materials, conductive agent, binding agent and adsorbent is 60%: 15%: 15%: 10%.Prepare anode pole piece and assembled battery by the method identical with embodiment 1, the battery charging and discharging test result shows, the first charge-discharge specific capacity of material is 867.4mAh/g, and 50 times circulation back specific capacity also remains on 535.6mAh/g, has shown good battery performance.

Embodiment 3

(wherein the pore-size distribution of carbide derived carbon is 0.5~5nm) as positive electrode active materials to select carbide derived carbon and sulphur composite material for use, mesoporous carbon prepares anode pole piece as sorbent material, and wherein the mass ratio of positive electrode active materials, conductive agent, binding agent and adsorbent is 75%: 10%: 10%: 5%.Prepare anode pole piece and assembled battery by the method identical with embodiment 1.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 924.1mAh/g, and 50 times circulation back specific capacity also remains on 607.9mAh/g, has shown good battery performance.

Embodiment 4

Select for use mesoporous carbon and sulphur composite material as positive electrode active materials, carbon molecular sieve prepares anode pole piece as sorbent material, and wherein the mass ratio of positive electrode active materials, conductive agent, binding agent and adsorbent is 60%: 15%: 15%: 10%.Prepare anode pole piece and assembled battery by the method identical with embodiment 1.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is mAh/g, and 50 times circulation back specific capacity also remains on mAh/g, has shown good battery performance.

Embodiment 5

Select for use mesoporous carbon and sulphur composite material as positive electrode active materials, macroporous absorbent resin Amberlite XAD-4 prepares anode pole piece as sorbent material, and wherein the mass ratio of positive electrode active materials, conductive agent, binding agent and adsorbent is 60%: 15%: 15%: 10%.Prepare anode pole piece and assembled battery by the method identical with embodiment 1.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 853.0mAh/g, and 50 times circulation back specific capacity also remains on 558.6mAh/g, has shown good battery performance.

Embodiment 6

Select FeS for use 2As positive electrode active materials, (pore-size distribution 0.5~5nm) is prepared into anode pole piece as adsorbent to the carbide derived carbon, and wherein the mass ratio of positive electrode active materials, conductive agent, binding agent and adsorbent is 50%: 20%: 20%: 10%.Electrolyte is the LiCF of 1mol/L 3SO 3(1: 1 volume ratio, TGM: tetraethyleneglycol dimethyl ether, DOL: dioxolanes), the anode pole piece preparation is identical with the method for embodiment 1 with the battery assembling for/TGM: DOL.

Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 752.6mAh/g, and 50 times circulation back specific capacity also remains on 566.9mAh/g, has shown good battery performance.

Embodiment 7

Except selecting for use NiS, prepare anode pole piece and assembled battery by the method identical with embodiment 6 as the positive electrode active materials.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 641.2mAh/g, and 50 times circulation back specific capacity also remains on 493.7mAh/g, has shown good battery performance.

The comparative example

Referring to Fig. 1, traditional anode pole piece is made up of positive electrode active materials, conductive agent and binding agent.In the cell preparation process, do not add adsorbent.Positive electrode active materials is carbon nano-tube and sulphur composite material, the mass ratio of positive electrode active materials, conductive agent and binding agent is 75%: 15%: 10%, select for use acetylene black as conductive agent equally, the PVDF of 5wt% (Kynoar) solution (solvent is NMP, the N-methyl pyrrolidone) is made the anodal slip of adhesive preparation.Slip is coated in is prepared into anode pole piece on the nickel foam, oven dry promptly obtains required anode pole piece, and the thickness of anode pole piece is 45~55um.Select for use the Celgard2400 film to be assembled into battery, the LiPF of electrolyte 1mol/L as battery diaphragm 6/ EC: DMC (1: 1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate).

The resulting battery charging and discharging test result of each embodiment and Comparative Examples is presented in the table 1.

Table 1

As seen from Table 1, added each embodiment of sorbing material in the positive electrode, compared with the comparative example, the specific capacity of battery and cycle performance have all had significant raising.

The lithium-sulfur cell that the present invention has added adsorbent can adsorb the polysulfide that be dissolved in the electrolyte by the suction-operated of sorbing material, improves the serviceability and the cycle life of lithium-sulfur cell.

Claims (10)

1. a positive pole plate of lithium-sulfur cell comprising positive electrode active materials, conductive agent and binding agent, is characterized in that, has added adsorbent in this anode pole piece, and the adsorbent addition is more than 5% of anode pole piece quality.
2. positive pole plate of lithium-sulfur cell according to claim 1 is characterized in that, the quality percentage composition of described anode pole piece is: positive electrode active materials 50%~75%, and conductive agent 10%~20%, binding agent 10%~20%, adsorbent are 5%~15%.
3. positive pole plate of lithium-sulfur cell according to claim 1 is characterized in that described adsorbent is dispersed among the anode pole piece material.
4. according to claim 1 or 2 or 3 described positive pole plate of lithium-sulfur cell, it is characterized in that, described adsorbent is the porous adsorbing material with high-specific surface area: active carbon, carbosphere, mesoporous carbon, carbon molecular sieve, carbide derived carbon or polymeric adsorbent, carbide derived carbon pore-size distribution is 0.5~5nm.
5. positive pole plate of lithium-sulfur cell according to claim 1, it is characterized in that, described positive electrode active materials is carbon sulphur composite material or metal sulfide, and wherein carbon is active carbon, carbon nano-tube, mesoporous carbon or carbide derived carbon in the carbon sulphur composite material, and described metal sulfide is FeS 2Or NiS.
6. according to right 1 described positive pole plate of lithium-sulfur cell, it is characterized in that described binding agent is the Kynoar solution of 15wt%, this solution solvent is the N-methyl pyrrolidone.
7. according to right 1 described positive pole plate of lithium-sulfur cell, it is characterized in that described conductive agent is with acetylene black or superconduction carbon black.
8. lithium-sulfur cell, it is characterized in that, this lithium-sulfur cell is assembled into negative pole and barrier film by the described anode pole piece of claim 1, positive pole uses aluminium flake to be collector, negative pole uses copper sheet to make collector, and negative pole is selected metal lithium sheet, Li and Si alloy, Li and Sn alloy or Li and C alloy for use.
9. lithium-sulfur cell according to claim 8 is characterized in that, described barrier film is the polypropylene and the polyethylene duplicature of porous.
10. lithium-sulfur cell according to claim 8, it is characterized in that electrolyte is nonaqueous electrolytic solution, solvent is dimethyl carbonate and methyl ethyl carbonate mixed solvent, perhaps butyl oxide link and tetraethyleneglycol dimethyl ether mixed solvent, solute is lithium hexafluoro phosphate or trifluoromethyl sulfonic acid lithium.
CN2011100862086A 2011-04-07 2011-04-07 Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery CN102185127A (en)

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CN102903974A (en) * 2012-10-22 2013-01-30 中国电子科技集团公司第十八研究所 Lithium-sulfur secondary battery
CN102945966A (en) * 2012-12-07 2013-02-27 中国科学院上海硅酸盐研究所 Positive pole composite system of lithium sulphur battery containing catalytic additive
CN103500848A (en) * 2013-10-02 2014-01-08 中国地质大学(武汉) Battery additive, positive material containing additive and preparation method of positive material
CN103762347A (en) * 2014-01-24 2014-04-30 上海理工大学 Electrode material and preparation method thereof
CN103855357A (en) * 2012-12-04 2014-06-11 中国科学院大连化学物理研究所 Electrode structure of lithium-sulfur battery as well as preparation and application of electrode structure
CN103849001A (en) * 2012-12-04 2014-06-11 中国科学院大连化学物理研究所 Composite membrane for lithium sulphur battery and preparation method thereof
CN104620416A (en) * 2012-08-17 2015-05-13 得克萨斯州大学系统董事会 Porous carbon interlayer for lithium-sulfur battery
CN104900830A (en) * 2015-06-29 2015-09-09 北京理工大学 Lithium-sulfur battery with carbon fiber cloth as barrier layer
CN105506310A (en) * 2016-01-07 2016-04-20 李震祺 Method for extracting lithium from lithium-containing brine
CN105702944A (en) * 2016-02-03 2016-06-22 宁波良能新材料有限公司 Lithium-sulfur battery
US20160248087A1 (en) * 2013-10-18 2016-08-25 Lg Chem, Ltd. Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same
CN106328883A (en) * 2016-10-24 2017-01-11 贵州梅岭电源有限公司 Lithium thionyl chloride battery positive electrode and preparation method thereof
CN106450224A (en) * 2016-11-21 2017-02-22 湘潭大学 Macroporous adsorptive resin based anode composite material for lithium-sulfur battery and preparation method thereof
CN106716702A (en) * 2014-09-26 2017-05-24 株式会社Lg 化学 Lithium-sulfur battery and battery module including same
CN106920943A (en) * 2017-04-10 2017-07-04 深圳市佩成科技有限责任公司 A kind of Ti3C2TxThe types of/SBA 15 are classified sulphur carbon composite
CN107910584A (en) * 2017-10-23 2018-04-13 西安理工大学 A kind of production method of Soft Roll lithium-sulfur cell
CN108054377A (en) * 2017-12-27 2018-05-18 湖南工业大学 A kind of preparation method and lithium-sulfur cell of knitting wool Spherical Carbon/sulphur composite microsphere material
CN109802137A (en) * 2018-12-18 2019-05-24 桑德集团有限公司 Lithium-sulfur cell binder and preparation method thereof, anode sizing agent and preparation method thereof

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CN104620416A (en) * 2012-08-17 2015-05-13 得克萨斯州大学系统董事会 Porous carbon interlayer for lithium-sulfur battery
CN102903974B (en) * 2012-10-22 2017-05-03 中国电子科技集团公司第十八研究所 Lithium-sulfur secondary battery
CN102903974A (en) * 2012-10-22 2013-01-30 中国电子科技集团公司第十八研究所 Lithium-sulfur secondary battery
CN103855357B (en) * 2012-12-04 2016-01-13 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell electrode structure and Synthesis and applications thereof
CN103855357A (en) * 2012-12-04 2014-06-11 中国科学院大连化学物理研究所 Electrode structure of lithium-sulfur battery as well as preparation and application of electrode structure
CN103849001B (en) * 2012-12-04 2016-05-04 中国科学院大连化学物理研究所 A kind of composite membrane and preparation method thereof for lithium-sulfur cell
CN103849001A (en) * 2012-12-04 2014-06-11 中国科学院大连化学物理研究所 Composite membrane for lithium sulphur battery and preparation method thereof
CN102945966A (en) * 2012-12-07 2013-02-27 中国科学院上海硅酸盐研究所 Positive pole composite system of lithium sulphur battery containing catalytic additive
CN103500848A (en) * 2013-10-02 2014-01-08 中国地质大学(武汉) Battery additive, positive material containing additive and preparation method of positive material
US20160248087A1 (en) * 2013-10-18 2016-08-25 Lg Chem, Ltd. Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same
US9911975B2 (en) * 2013-10-18 2018-03-06 Lg Chem, Ltd. Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same
CN103762347A (en) * 2014-01-24 2014-04-30 上海理工大学 Electrode material and preparation method thereof
CN103762347B (en) * 2014-01-24 2017-01-04 上海理工大学 A kind of electrode material and preparation method thereof
CN106716702A (en) * 2014-09-26 2017-05-24 株式会社Lg 化学 Lithium-sulfur battery and battery module including same
US10615462B2 (en) 2014-09-26 2020-04-07 Lg Chem, Ltd. Lithium-sulfur battery and battery module including same
CN104900830A (en) * 2015-06-29 2015-09-09 北京理工大学 Lithium-sulfur battery with carbon fiber cloth as barrier layer
CN105506310A (en) * 2016-01-07 2016-04-20 李震祺 Method for extracting lithium from lithium-containing brine
CN105702944B (en) * 2016-02-03 2017-06-30 江苏金阳光新能源科技有限公司 A kind of lithium-sulfur cell
CN105702944A (en) * 2016-02-03 2016-06-22 宁波良能新材料有限公司 Lithium-sulfur battery
CN106328883A (en) * 2016-10-24 2017-01-11 贵州梅岭电源有限公司 Lithium thionyl chloride battery positive electrode and preparation method thereof
CN106450224A (en) * 2016-11-21 2017-02-22 湘潭大学 Macroporous adsorptive resin based anode composite material for lithium-sulfur battery and preparation method thereof
CN106450224B (en) * 2016-11-21 2019-03-08 湘潭大学 A kind of anode composite material of lithium sulfur battery and preparation method thereof based on macroporous absorbent resin
CN106920943A (en) * 2017-04-10 2017-07-04 深圳市佩成科技有限责任公司 A kind of Ti3C2TxThe types of/SBA 15 are classified sulphur carbon composite
CN106920943B (en) * 2017-04-10 2019-11-15 深圳市佩成科技有限责任公司 A kind of Ti3C2Tx/ SBA-15 type is classified sulphur carbon composite
CN107910584A (en) * 2017-10-23 2018-04-13 西安理工大学 A kind of production method of Soft Roll lithium-sulfur cell
CN108054377A (en) * 2017-12-27 2018-05-18 湖南工业大学 A kind of preparation method and lithium-sulfur cell of knitting wool Spherical Carbon/sulphur composite microsphere material
CN109802137A (en) * 2018-12-18 2019-05-24 桑德集团有限公司 Lithium-sulfur cell binder and preparation method thereof, anode sizing agent and preparation method thereof

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Application publication date: 20110914