CN104795592B - A kind of polymer lithium-sulfur cell and preparation method thereof - Google Patents

A kind of polymer lithium-sulfur cell and preparation method thereof Download PDF

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CN104795592B
CN104795592B CN201510200961.1A CN201510200961A CN104795592B CN 104795592 B CN104795592 B CN 104795592B CN 201510200961 A CN201510200961 A CN 201510200961A CN 104795592 B CN104795592 B CN 104795592B
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lithium
polymer
solid
sulfur cell
conductive agent
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CN104795592A (en
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康飞宇
柳明
周栋
贺艳兵
李宝华
游从辉
杜鸿达
杨全红
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Shenzhen Graphene Innovation Center Co., Ltd.
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Shenzhen Graduate School Tsinghua University
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 present invention provides a kind of polymer lithium-sulfur cell and preparation method thereof, and the polymer lithium sulphur battery includes：Positive pole：Sulfenyl active material, conductive agent, binding agent；Negative pole：Active material, conductive agent, binding agent；Electrolyte：Using polymer dielectric, including solid solvent and liquid flux combination, lithium salts, cross-linking monomer and initiator.Polymer lithium sulphur battery energy density height prepared by the present invention, security performance height, stable chemical performance, production cost are low, have less polarization in charge and discharge process, and capacity keeps stable, with good application prospect.

Description

A kind of polymer lithium-sulfur cell and preparation method thereof
Technical field
The invention belongs to polymer lithium sulphur cell manufacturing techniques field, more particularly to a kind of new polymers battery and its should With.
Background technology
Mankind's modern life be unable to do without moveable electrochmical power source, and lithium ion battery is due to environment-friendly, work electricity The advantages of pressure is high, specific capacity is big and has extended cycle life and be widely used in all kinds of Miniature Portable Units, as the world today Extremely potential novel green electrochmical power source.However, with the raising of life taste, people propose to mobile electrical appliance Higher demand：It is lighter, thinner, smaller, more longlasting；Therefore as the power supply unit of these portable power sources, to lithium ion battery Requirement also accordingly increase.But the lithium ion battery of traditional form be difficult to meet people will for the items of electrochmical power source Ask, the lithium ion battery of future generation of high-energy-density is among the upsurge of extensive exploitation, and lithium-sulfur cell is as by industrial circle And the good lithium ion battery of new generation of academia is gradually favored by people.But lithium-sulfur cell is exposed on stream The problems come also are badly in need of solving：Such as, during sulphur is as positive active material in its relatively low electronic conductivity, cyclic process Between product polysulfide dissolving, in addition, Volume Changes of the sulfur electrode during embedding de- lithium all be restriction lithium-sulfur cell development Main cause.
In the last few years, in order to solve the above problems, people prepare various dimensions, multiple dimensioned new carbon and sulphur are carried out Match somebody with somebody.Although novel carbon-sulfur composite can effectively improve the electronic conductivity of sulphur, and suppress polysulfide to a certain extent Dissolving, but nanoscale new carbon preparation technology is complicated, and reduces the energy density of overall sulfur electrode.Therefore, it is other The method of lithium-sulfur cell performance is improved among gradually developing.Wang[ChemElectroChem,2015,2(1):22-36.] etc. People thinks effectively suppress polysulfide dissolving using polymer dielectric in lithium-sulfur cell, so as to reduce in cyclic process Sulphur loss and polysulfide dissolving after the material such as the lithium sulfide that is generated repeatedly in negative terminal surface.But traditional lithium battery is universal Its electrical conductivity of the polymer dielectric used is low, preparation technology is complicated and the interface poor when being matched with sulfur electrode is compatible asks Topic all turns into the technological difficulties during polymer lithium-sulfur cell is developed.
Electrolyte and electrode match effectively reducing inside battery interface impedance using the method for in-situ polymerization Problem, but it is still subject matter that polymer dielectric is applied in lithium-sulfur cell that electrical conductivity is low.Therefore, how to improve poly- The electrical conductivity of polymer electrolyte takes into account the compatible problem in interface simultaneously, develops performance stabilization, high power density, high-energy-density Polymer lithium-sulfur cell, is the important topic in lithium-sulfur cell field, is also that current lithium-sulfur cell commercialized development is urgently to be resolved hurrily Technical barrier.
The content of the invention
In order to solve the above technical problems, a kind of performance stabilization of present invention offer, high power density, high-energy-density is poly- Compound lithium-sulfur cell.
A kind of polymer lithium-sulfur cell, including：
Positive pole：Sulfenyl active material, conductive agent, binding agent；
Negative pole：Active material, conductive agent, binding agent；
Electrolyte：Using polymer dielectric, including solid solvent and liquid flux combination, lithium salts, cross-linking monomer and draw Send out agent；
The cross-linking monomer includes following structure：
Wherein R1、R2For carbon number 1-20 straight chain Alkyl chain, the linear alkyl chain containing ether-oxygen bond, the one of which of the alkyl chain containing side base and the segment containing single phenyl ring, its Middle n >=2.The cross-linking monomer is purchased in E.I.Du Pont Company.
Preferably, the polymer dielectric is characterized in that, by weight percentage, the cross-linking monomer is 0.5- 20%；The initiator is 0.001-5%；The lithium salts is 1-20%, and surplus is solid-liquid solvent.
Preferably, in the positive pole, by weight percentage, sulfenyl active material accounts for the 70-99% of whole anode pole piece；Lead Electric agent accounts for the 0.5-20% of whole anode pole piece；Binding agent accounts for the 0.5-20% of whole anode pole piece.
Preferably, in the negative pole, by weight percentage, active material accounts for the 70-100% of whole cathode pole piece；It is conductive Agent accounts for the 0.5-20% of whole cathode pole piece；Conductive agent accounts for the 0.5-20% of whole cathode pole piece；
Preferably, in the positive pole, the positive pole sulfenyl active material is elemental sulfur, polysulfide (Li2Sn), it is organic At least one of sulfide and sulphur carbon composite；Conductive agent uses acetylene black, conductive black, Ketjen black, electrically conductive graphite, stone At least one of black alkene, CNT；Binding agent uses Kynoar, polyvinyl alcohol, polytetrafluoroethylene (PTFE), carboxymethyl cellulose At least one of plain sodium, polyolefin, polyurethane, butadiene-styrene rubber, acrylonitrile multiple copolymer.
Preferably, the active material in the negative pole uses lithium metal, or embedding lithium compound, lithium metal or prelithiation stone At least one of black, embedding lithium Si-C composite material, embedding lithium tin-carbon composite；Conductive agent uses acetylene black, conductive black, section Qin is black, at least one of electrically conductive graphite, graphene, CNT.
Preferably, the solid-liquid solvent is the mixture of solid solvent and liquid flux；The liquid flux uses carbonic acid Vinyl acetate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, tetrahydrofuran, ethylene glycol At least one of dimethyl ether, tetraethyleneglycol dimethyl ether and DOX；The solid solvent：Ethylene carbonate, carbonic acid At least one of diphenyl ester, di-tert-butyl dicarbonate, malononitrile, succinonitrile, stearonitrile and isophthalodinitrile.
Preferably, the lithium salts uses lithium hexafluoro phosphate, two (trifluoromethane sulfonic acid) imine lithiums, three (trimethyl fluoride sulfonyls) At least one of lithium methide, dioxalic acid lithium borate, three (pentafluoroethyl group) three lithium fluophosphate.
Accordingly, the present invention also provides a kind of preparation method of polymer lithium-sulfur cell, it is characterised in that including following step Suddenly：
Step A：The preparation of solid polymer electrolyte presoma：Cross-linking monomer, lithium salts, initiator addition solid-liquid is molten It is well mixed after agent, solid polymer electrolyte presoma is made；
Step B：Barrier film, positive pole diaphragm and cathode membrane are assembled into after naked battery core in glove box, enters shell or bag, obtains Treat fluid injection battery core；
Step C:Solid polymer electrolyte presoma injection made from step A, after being sealed after fluid injection battery core, is treated into diaphragm Fully after infiltration, trigger within 2-24 hours monomer polymerization in being heated at 0.1-10Pa, 50-100 DEG C, fabricated in situ solid polymer electricity Xie Zhi, is melted into, shaping, after degasification process, prepares the battery after shaping successively.
Polymer lithium sulphur battery energy density height prepared by the present invention, security performance height, stable chemical performance, production cost It is low, there is less polarization in charge and discharge process, and capacity keeps stable, with good application prospect.
Brief description of the drawings
The outward appearance photo for the polymer dielectric that Fig. 1 is prepared for the present invention.
Fig. 2 in the polymer dielectric for preparing of the present invention, in polymerized monomer active function groups number and its electrical conductivity and Relation between reversible specific capacity first.Number of monomers accounts for the 5% of whole precursor solution gross masses.
Thermogravimetric curve figures of the Fig. 3 for the polymer dielectric of the invention prepared in air atmosphere.
Cycle performances of the Fig. 4 for the polymer lithium-sulfur cell of the invention prepared under 0.5C/0.5C current densities.
High rate performances of the Fig. 5 for the polymer lithium-sulfur cell of the invention prepared under different current densities.
Embodiment
Below in conjunction with the accompanying drawings, the preferably embodiment to the present invention is described in further detail：
Embodiment 1
Step 1) following components is weighed by following relationship between quality, by weight, ethoxyquin tetramethylol methane tetraacrylate：Carbon Vinyl acetate:Diethyl carbonate:Methyl ethyl carbonate:Lithium hexafluoro phosphate：Lauroyl peroxide=5:30：20：30:14.9:0.1. By ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, well mixed, lithium hexafluoro phosphate is added afterwards, then by ethoxyquin season penta Tetra-acrylate, lauroyl peroxide add above-mentioned electrolyte and polymer dielectric presoma are made；
Step 2) prepare and treat fluid injection battery core：According to weight ratio, nanometer sulphur powder：Acetylene black：Kynoar is 70：25：5 Ratio weighs anode pole piece material；According to weight ratio, lithium intercalated graphite：Acetylene black：Kynoar is 90：5：5 ratio is weighed Cathode pole piece material, pole piece to be spooled is obtained by processes such as stirring, coating, cold pressing, slitting, welding, afterwards again with barrier film Winding obtains naked battery core together, the use of aluminum plastic film is that packaging bag carries out top side seal, is toasted afterwards in vacuum drying oven.
Polymer dielectric presoma injection made from step A after being sealed after fluid injection battery core, is treated that diaphragm fully soaks by step 3 After profit, monomer polymerization is triggered within 4 hours in being heated at 2Pa, 80 DEG C, fabricated in situ polymer dielectric is melted into, whole successively After shape, degasification process, the battery after shaping is prepared.
Embodiment 2
Step 1) following components is weighed by following relationship between quality, according to weight ratio, double pentaerythritol methacrylate：Second two Diethylene glycol dimethyl ether:1,3- dioxolanes:Base two (trifluoromethane sulfonic acid) imine lithium：Azodiisobutyronitrile=3:40:40：30:14.9: 0.1.Glycol dimethyl ether, DOX are well mixed, base two (trifluoromethane sulfonic acid) imine lithium is added afterwards, then will Double pentaerythritol methacrylate, azodiisobutyronitrile add above-mentioned electrolyte and polymer dielectric presoma are made；
Step 2) prepare and treat fluid injection battery core：According to weight ratio, sulphur carbon composite：CNT：Polytetrafluoroethylene (PTFE) is 70： 25：5 ratio weighs anode pole piece material, and pole piece to be spooled is obtained by processes such as stirring, coating, cold pressing, slitting, welding, Wound again together with barrier film and lithium piece afterwards and obtain naked battery core, the use of aluminum plastic film is that packaging bag carries out top side seal, afterwards true Toasted in empty baking oven.
Polymer dielectric presoma injection made from step A after being sealed after fluid injection battery core, is treated that diaphragm fully soaks by step 3 After profit, monomer polymerization is triggered within 4 hours in being heated at 0.5Pa, 70 DEG C, fabricated in situ solid polymer electrolyte is changed successively Into after, shaping, degasification process, the battery after shaping is prepared.
Embodiment 3
Step 1) following components is weighed by following relationship between quality, according to weight ratio, succinonitrile：Acrylonitrile replaces polyethylene Alcohol：Lithium hexafluoro phosphate：Boron trifluoride=75:10:14.9:0.1.By succinonitrile in heating melting at 50 DEG C, acrylonitrile is replaced Polyvinyl alcohol, lithium hexafluoro phosphate, boron trifluoride are added after nitrile melt and are well mixed, and full solid state polymer electrolyte forerunner is made Body；
Step 2) prepare and treat fluid injection battery core：According to organic sulfur compound：Graphene：Sodium carboxymethylcellulose is 70：25：5 Ratio weighs anode pole piece material；According to embedding lithium Si-C composite material：Graphene：Sodium carboxymethylcellulose is 90：5：5 ratio Weigh cathode pole piece material, it is mixed to obtain pole piece to be spooled by processes such as stirring, coating, cold pressing, slitting, welding, afterwards again with Barrier film is wound together obtains naked battery core, the use of aluminum plastic film is that packaging bag carries out top side seal, is dried afterwards in vacuum drying oven It is roasting.
Polymer dielectric presoma injection made from step A after being sealed after fluid injection battery core, is treated that diaphragm fully soaks by step 3 After profit, at 4Pa, 80 DEG C heat 24 hours, fabricated in situ solid polymer electrolyte, be melted into successively, shaping, degasification work After sequence, the battery after shaping is prepared.
Comparative example 1
Prepare liquid electrolyte：It is stand-by that following components is weighed by following mass ratio relation：Glycol dimethyl ether:1,3- bis- Butyl oxide link=50：50, base two (trifluoromethane sulfonic acid) imine lithium is added afterwards, obtains base two (trifluoromethane sulfonic acid) imine lithium Concentration is 1mol/L electrolyte.
Fluid injection battery core is treated in preparation：Using nanometer sulphur powder as active material, conductive agent, bonding agent are added, by stirring, is applied Cover, be cold-pressed, slitting, the process such as welding obtain pole piece to be spooled, being wound again together with barrier film and lithium piece obtain naked battery core afterwards, The use of aluminum plastic film is that packaging bag carries out top side seal, is toasted afterwards in vacuum drying oven.
Fluid injection and anode ring forming：Above-mentioned electrolyte is injected in the battery core after baking, stood until electrolyte fully infiltrates Whole diaphragm, then be melted into, shaping, the process such as degasification, finally give the battery after shaping.
Embodiment 1-3 and comparative example 1 are tested as follows：
Volume test：Volume test is carried out to each embodiment and the battery core of comparative example by following flow in 25 DEG C of environment： Stand 3min；0.1C constant currents are put a little to 1.5V；Stand 3min；0.1C constant-current charges obtain discharge capacity first to 3.0V；Stand Volume test is completed after 3min.
Multiplying power is tested：Multiplying power test is carried out to each embodiment and the battery core of comparative example by following flow in 25 DEG C of environment：
Drift bolt is tested：Each embodiment and the battery core of comparative example are completely filled by following flow in 25 DEG C of environment：Stand 3min； 0.1C constant-current discharges are to 1.5V, constant-voltage charge to 0.05C；It is fixed in afterwards on special drift bolt fixture, using a diameter of 2.5mm iron nail, with 10mm/s speed through battery core center, statistics battery core is caught fire quantity；Simultaneously during drift bolt, prison The heating curve of drift bolt position is controlled, the maximum of T in the battery core heating curve that do not catch fire is recordedmax。
Performance is as shown in table 1：
Table 1
The outward appearance photo for the polymer dielectric that Fig. 1 is prepared for the present invention, is rendered as white gels shape；Fig. 2 shows currently The timing of monomer ratio one in body solution, its polymer dielectric electrical conductivity and first reversible specific capacity are with active in polymerized monomer Functional group number purpose increases and increased.
Polymer lithium-sulfur cell prepared by the present invention, Room-temperature-conductivity of Polymer Electrolyte may be up to 10-2S/cm, fills first Electric discharge reversible capacity reaches 1150mAh/g；Fig. 3 shows that polymer dielectric prepared by the present invention is heated in air atmosphere 300 DEG C of mass losses 11.5%, in contrast to this conventional electrolysis liquid 300 DEG C lose 46.2%, show gel polymer electrolyte With good heat endurance；Fig. 4 shows polymer lithium-sulfur cell filling under 0.5C/0.5C current densities prepared by the present invention Discharge cycle performance figure, capacity is not almost decayed after 300 circulations, and battery polarization is small, and coulombic efficiency is up to more than 99%, figure Reversible capacity remains to play under the circulation curve map of the 5 polymer lithium-sulfur cells prepared for the present invention, 2C current densities Reversible capacity remains to play more than 60% under 0.1C under more than 90%, 5C current densities under 0.1C.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention, On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's Protection domain.

Claims (6)

1. a kind of polymer lithium-sulfur cell, it is characterised in that including：
Positive pole：Sulfenyl active material, conductive agent, binding agent；
Negative pole：Active material, conductive agent, binding agent；
Electrolyte：Using polymer dielectric, the polymer dielectric includes solid-liquid solvent, lithium salts, cross-linking monomer and initiation Agent;
The cross-linking monomer includes following structure：Or, wherein R1, R2 is that carbon is former Subnumber 1-20 linear alkyl chain, the linear alkyl chain containing ether-oxygen bond, the alkyl chain containing side base and the chain containing single phenyl ring The one of which of section, wherein n >=2；
By weight percentage, the cross-linking monomer is 0.5-20% to the polymer dielectric；The initiator is 0.001-5%； The lithium salts is 1-20%, and surplus is solid-liquid solvent；
The solid-liquid solvent is made up of solid solvent and liquid flux；The liquid flux uses ethylene carbonate, propylene carbonate Ester, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, tetrahydrofuran, glycol dimethyl ether, tetraethylene glycol At least one of dimethyl ether and DOX；The solid solvent uses diphenyl carbonate, di-tert-butyl dicarbonate, third At least one of dintrile, succinonitrile, stearonitrile and isophthalodinitrile.
2. polymer lithium-sulfur cell as claimed in claim 1, it is characterised in that in the positive pole, by weight percentage, sulfenyl Active material accounts for the 70-99% of whole anode pole piece；Conductive agent accounts for the 0.5-20% of whole anode pole piece；Binding agent accounts for whole positive pole The 0.5-20% of pole piece.
3. polymer lithium-sulfur cell as claimed in claim 1, it is characterised in that in the negative pole, by weight percentage, activity Material accounts for the 70-100% of whole cathode pole piece；Conductive agent accounts for the 0.5-20% of whole cathode pole piece；Conductive agent accounts for whole negative pole pole The 0.5-20% of piece.
4. polymer lithium-sulfur cell as claimed in claim 1, it is characterised in that in the positive pole, the positive pole sulfenyl activity Material is at least one of elemental sulfur, polysulfide, organic sulfur compound and sulphur carbon composite；Conductive agent uses acetylene At least one of black, conductive black, Ketjen black, electrically conductive graphite, graphene, CNT；Binding agent using Kynoar, In polyvinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyolefin, polyurethane, butadiene-styrene rubber, acrylonitrile multiple copolymer At least one.
5. polymer lithium-sulfur cell as claimed in claim 1, it is characterised in that the lithium salts uses lithium hexafluoro phosphate, two（Three Methyl fluoride sulfonic acid）Imine lithium, three（Trimethyl fluoride sulfonyl）Lithium methide, dioxalic acid lithium borate, three（Pentafluoroethyl group）Three lithium fluophosphates At least one of.
6. a kind of method for preparing polymer lithium-sulfur cell as claimed in claim 1, it is characterised in that comprise the following steps：
Step A：The preparation of solid polymer electrolyte presoma：Cross-linking monomer, lithium salts, initiator are added after solid-liquid solvent It is well mixed, solid polymer electrolyte presoma is made；
Step B：Barrier film, positive pole diaphragm and cathode membrane are assembled into after naked battery core in glove box, enter shell or bag, obtains waiting to note Liquid battery core；
Step C:By solid polymer electrolyte presoma injection made from step A after sealing after fluid injection battery core,
After diaphragm fully infiltrates, monomer polymerization is triggered within 2-24 hours in being heated at 0.1-10Pa, 50-100 DEG C, fabricated in situ is solid State polymer dielectric, is melted into, shaping, after degasification process, prepares the battery after shaping successively.
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CN106876783B (en) * 2015-12-10 2019-07-05 中国科学院大连化学物理研究所 A kind of all solid state lithium-sulfur cell
CN107845771A (en) * 2016-09-21 2018-03-27 中国科学院大连化学物理研究所 The anode composite and its preparation and chemical cell of a kind of sulphur and manganese dioxide
CN106532115A (en) * 2016-11-25 2017-03-22 张家港市国泰华荣化工新材料有限公司 Gel electrolyte and lithium-sulfur secondary battery
CN109103500B (en) * 2017-06-20 2020-05-26 中国科学院化学研究所 Polymer lithium selenium battery and preparation method thereof
CN109244527A (en) * 2017-07-11 2019-01-18 罗伯特·博世有限公司 A kind of solid secondary batteries and preparation method thereof based on silicon substrate anode
CN109659474A (en) * 2017-10-12 2019-04-19 宁德时代新能源科技股份有限公司 Rigid diaphragm and solid-state lithium metal battery
CN109873199B (en) * 2017-12-01 2021-11-16 中国科学院大连化学物理研究所 Polymer dispersion liquid and application thereof
CN108281704B (en) * 2018-01-22 2020-02-21 厦门大学 Solid electrolyte composite material and preparation method and application thereof
CN109361009A (en) * 2018-10-19 2019-02-19 浙江大学 A kind of sulphur-silicon lithium battery
CN111244492B (en) * 2020-02-29 2021-11-09 同济大学 High-specific-energy primary lithium-sulfur battery and application thereof
CN113540574A (en) * 2021-06-24 2021-10-22 西安交通大学 Lithium battery assembly process for heating in-situ solidified electrolyte

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