CN109411809A - A kind of preparation method of low temperature flexibility solid polyelectrolyte film and its application in low-temperature solid lithium ion battery - Google Patents
A kind of preparation method of low temperature flexibility solid polyelectrolyte film and its application in low-temperature solid lithium ion battery Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000867 polyelectrolyte Polymers 0.000 title description 18
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 239000010954 inorganic particle Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 229920005570 flexible polymer Polymers 0.000 claims abstract 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 29
- 239000004800 polyvinyl chloride Substances 0.000 claims description 27
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 20
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000123 paper Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 6
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 6
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical group N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013423 LiN(SO2F)2 (LiFSI) Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 239000011267 electrode slurry Substances 0.000 claims 2
- 239000011888 foil Substances 0.000 claims 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011086 glassine Substances 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 hydrogen furans Chemical class 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QGFUJXDXUWUFJG-UHFFFAOYSA-N lithium;perchloric acid Chemical compound [Li].OCl(=O)(=O)=O QGFUJXDXUWUFJG-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种低温柔性聚合物固态电解质膜的制备方法及其在低温固体锂离子电池中的应用，属于固体锂离子电池技术领域。本发明的技术方案要点为：将聚合物质量5%~20%的锂盐和聚合物质量10%~50%的增塑剂混合后加入溶剂中并充分溶解，再将聚合物质量10%~90%的无机颗粒与溶剂混合球磨后加入到上述溶液中，所得溶液经过刮涂或流延涂覆于载体上，于60~120℃烘干后即得厚度为20~100μm的低温柔性聚合物固态电解质膜。本发明还公开了该低温柔性聚合物固态电解质膜在低温固体锂离子电池中的应用。本发明制备的低温固态锂离子电池中使用的聚合物固体电解质膜在低温下具有良好的电导率和柔韧性，从而使得制备低温下能够高效、稳定、安全循环的固态锂离子电池成为可能。
The invention discloses a preparation method of a low temperature flexible polymer solid electrolyte membrane and its application in a low temperature solid lithium ion battery, belonging to the technical field of solid lithium ion batteries. The main points of the technical solution of the present invention are as follows: the lithium salt of 5% to 20% of the polymer mass and the plasticizer of 10% to 50% of the polymer mass are mixed, then added to the solvent and fully dissolved, and then 10% to 50% of the polymer mass is added to the solvent. 90% of the inorganic particles and the solvent are mixed and ball-milled and added to the above solution. The obtained solution is coated on the carrier by scraping or casting, and dried at 60-120 °C to obtain a low-temperature flexible polymer with a thickness of 20-100 μm. solid electrolyte membrane. The invention also discloses the application of the low temperature flexible polymer solid electrolyte membrane in the low temperature solid lithium ion battery. The polymer solid electrolyte membrane used in the low-temperature solid-state lithium-ion battery prepared by the invention has good electrical conductivity and flexibility at low temperature, thereby making it possible to prepare a solid-state lithium-ion battery capable of efficient, stable and safe cycling at low temperature.
Description
Technical field
The invention belongs to solid Li-ion battery technical fields, and in particular to a kind of low temperature flexibility solid polyelectrolyte
The preparation method of film and its application in low-temperature solid lithium ion battery.
Background technique
With the development and progress of society, the demands such as electric car and power grid energy storage are more more and more urgent, and exploitation uses temperature
The battery wide, safety is good, energy density and power are high becomes inexorable trend.In various commercialized secondary charge and discharge devices
In, most potential is lithium ion battery.Current commercialized lithium ion battery mainly based on liquid electrolyte, mainly at
Subpackage contains LiPF6, lithium salts such as LiFSI and with cyclic carbonate (EC, PC), linear carbonate (DEC, DMC, EDC), carboxylic acid esters
Organic solvent based on (MF, MA, EA, MP etc.).Liquid electrolyte conductivity at room temperature with higher, can efficiently soak
Moisten electrode particle, therefore such battery has the low internal resistance of cell and preferable cyclical stability and forthright again near room temperature
Energy.But liquid can occur at low temperature and convert admittedly for this kind of organic electrolyte, and conductivity is caused sharply to decline, when low temperature (- 20 DEG C with
Under) internal resistance of cell can significantly increase, it is unable to satisfy cryogenic applications requirement.In addition, commonly using the electrification of organic electrolyte system at present
It learns window and is generally less than 4.5V, influence the application of high-voltage anode material, limit the raising of battery energy density.
In solid-state but substance that Ion transfer can occur as liquid is known as solid electrolyte, since which employs solid
State structure, therefore replace traditional liquid electrolyte that can efficiently solve the above problem using solid electrolyte.In solid-state electricity
Xie Zhizhong, and it is divided into inorganic solid electrolyte and organic solid-state electrolyte.Both compare, organic polyelectrolyte has preferably
Elasticity, flexibility can reduce contact resistance admittedly, be more favorable to process, but its voltage window is narrow；Inorganic particle usually has
Still poor in processability, contact impedance are big for wider electrochemical window.The compound method of the two, which is usually taken, can be improved solid-state electricity
Solve the electrical property of matter.But problems are still faced in practical application production, including polymer solid under low temperature
The problem of electrolytic conductivity is relatively low and bad mechanical property.
Therefore, find one kind still can keep the solid electrolyte membrane of high degree of flexibility to necessitate at low temperature.Make
Solid lithium ion battery of good performance is assembled with the dielectric film with high conductance and stronger mechanical performance under low temperature
This scheme also provides new power for the application of solid state battery.
Summary of the invention
The main object of the present invention is to solve the problems such as current solid electrolyte membrane low-temperature conductivity is low and flexible poor, is provided
A kind of preparation method of low temperature flexibility solid polyelectrolyte film and its application in low temperature solid-state lithium ion battery.
The present invention adopts the following technical scheme that achieve the above object, a kind of low temperature flexibility solid polyelectrolyte film
Preparation method, it is characterised in that detailed process are as follows: by the increasing of the lithium salts of polymer quality 5% ~ 20% and polymer quality 10% ~ 50%
It is added in solvent after modeling agent mixing and sufficiently dissolves, then by the inorganic particle of polymer quality 10% ~ 90% and solvent mixing and ball milling
After be added in above-mentioned solution, acquired solution is coated on carrier by blade coating or curtain coating, up to thick after 60 ~ 120 DEG C of drying
The low temperature flexibility solid polyelectrolyte film that degree is 20 ~ 100 μm；
The polymer is modified polyvinyl chloride TPE or modified polyvinyl chloride TPE and polyvinylchloride, polyvinyl fluoride PVF, gathers
Vinyl chloride PVC, nitrile rubber NBR, modified polyvinyl chloride TPE, natural rubber NB or Kynoar-hexafluoropropene PVDF-HFP
One of or a variety of mixtures；
The lithium salts is LiN (SO2CF3)2(LiTFSI), LiN (SO2F)2(LiFSI), LiB (C2O4)2(LiBOB), LiBC2O4F2
(LiDFOB) or LiClO4One of or it is a variety of；
The plasticizer is succinonitrile (SN), diethyl phthalate (DEP), ethylene carbonate (EC), propene carbonate
(PC), one of polyethylene glycol dimethyl ether (PEGDME) or kaolin or a variety of；
The solvent is N-Methyl pyrrolidone (NMP), acetonitrile, acetone, ethyl acetate, N,N-dimethylformamide (DMF), four
One of hydrogen furans (THF) or dimethyl acetamide (DMAC) are a variety of；
The inorganic particle is LLZO, Al2O3, one of LAGP or LATP or a variety of；
The carrier is one of aluminium foil, copper foil, silicone oil paper or glaxin release paper.
Further preferably, the polymer is preferably modified polyvinyl chloride TPE, modified polyvinyl chloride TPE and lithium salts
For mass ratio in 10:1 ~ 3, gained low temperature flexibility solid polyelectrolyte film has preferable cryogenic property, and the low temperature flexibility is poly-
The density for closing object solid electrolyte membrane is the half of polychloroethylene film, tensile strength and tearing strength be respectively 20-25MPa and
50-60KN/m, brittle point is -65 DEG C ~ -75 DEG C, and polychloroethylene film is only gained low temperature flexibility polymer at -40 DEG C, -15 DEG C
The order of magnitude of solid electrolyte membrane conductivity reaches 10-4S/cm。
The preparation method of low temperature flexibility solid polyelectrolyte film of the present invention, it is characterised in that specific steps
Are as follows:
Step S1: taking modified polyvinyl chloride TPE 2g and lithium salts LiTFSI 1g to be dissolved in solvents tetrahydrofurane and is stirred
It is even to obtain clarification viscous solution；
Step S2: plasticizer phthalic acid diethylester DEP 1g is added in the viscous solution obtained to step S1, is sufficiently stirred
It is uniformly mixed and obtains solution A；
Step S3: by inorganic particle LLZO 1.2g and tetrahydrofuran mixing and ball milling, mixed system B is obtained after fully dispersed；
Step S4: the mixed system B that step S3 is obtained is added in the solution A that step S2 is obtained, after being sufficiently mixed uniformly
To dispersion C；
Step S5: the dispersion C that step S4 is obtained is prolonged into stream film forming in silicone oil paper, is put into vacuum drying oven after natural drying
In 60 DEG C of dry 12h, then the isolated low temperature flexibility solid polyelectrolyte film from silicone oil paper.
Application of the low temperature flexibility solid polyelectrolyte film of the present invention in low-temperature solid lithium ion battery,
It is characterized in that detailed process are as follows: be attached at after cutting the size of the low temperature flexibility solid polyelectrolyte film as required
On positive plate, then negative electrode tab lithium piece is covered, then assembled up to low-temperature solid lithium ion battery.
Further preferably, the specific preparation process of the positive plate are as follows: by positive electrode, conductive agent, lithium salts and binder
70 ~ 90:1 in mass ratio ~ 5:4 ~ 10:5 ~ 15 is added in solvent after mixing, and anode sizing agent is obtained after fully dispersed, by anode sizing agent
It is toasted in 100 ~ 120 DEG C after being coated on the aluminium foil with a thickness of 10 ~ 20 μm up to for assembling low temperature solid-state lithium ion battery just
Pole piece, the positive electrode are one of LiFePO4, LiMn2O4, cobalt acid lithium or three metaclass materials, and the binder is fourth
Nitrile rubber NBR, modified polyvinyl chloride TPE, natural rubber NB, Kynoar-hexafluoropropene PVDF-HFP or Kynoar
One of PVDF or a variety of, the conductive agent are one of the black SP of conductive acetylene, carbon pipe or graphene or a variety of, described molten
Agent is NMP.
Compared to conventional liquid lithium ion battery, consolidating based on low temperature flexibility solid polyelectrolyte film prepared by the present invention
State lithium ion battery not only overcomes the drawbacks of battery leakage, but also since the dielectric film has excellent low-temperature flexibility and leads
The advantages that electrical property, is conducive to the popularization and use of solid lithium ion battery at low ambient temperatures.
Polymer solid electrolyte film used in low temperature solid-state lithium ion battery prepared by the present invention has at low temperature
Good conductivity and flexibility, being capable of efficient, stabilization, the solid lithium ion battery recycled safely under low temperature so that preparing
It is possibly realized.
Detailed description of the invention
Fig. 1 is the ionic conductivity figure of the solid electrolyte in embodiment 1 and comparative example；
Fig. 2 is -20 DEG C of low temperature of cycle performance figure of the solid lithium ion battery in embodiment 1 and comparative example.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
The preparation of positive plate:
According to the mass percent of 80:3:7:10, by iron phosphate serving as positive active material, conductive agent acetylene black, lithium salts perchloric acid
Lithium and binder modification polyvinyl chloride TPE are added in appropriate solvent NMP, are tuned into slurry, are coated on aluminium foil after ball milling, so
After be put in baking oven in 80 DEG C of dry 30min, then in vacuum drying oven in 110 DEG C drying obtain positive plate for 24 hours.
The preparation method of low temperature flexibility solid polyelectrolyte film comprises the following steps:
Step S1: modified polyvinyl chloride TPE 2g and lithium salts LiTFSI 1g is taken to be dissolved in appropriate solvents tetrahydrofurane and stirring evenly
Obtain clarification viscous solution；
Step S2: plasticizer phthalic acid diethylester DEP 1g is added in the viscous solution obtained to step S1, is sufficiently stirred
It is uniformly mixed and obtains solution A；
Step S3: by inorganic particle LLZO 1.2g and tetrahydrofuran mixing and ball milling, mixed system B is obtained after fully dispersed；
Step S4: the mixed system B that step S3 is obtained is added in the solution A that step S2 is obtained, is divided after being sufficiently mixed
Granular media system C；
Step S5: the dispersion C that step S4 is obtained is prolonged into stream film forming in silicone oil paper, is put into vacuum drying oven after natural drying
In 60 DEG C of dry 12h, can from silicone oil paper isolated low temperature flexibility solid polyelectrolyte film.
Fig. 1 gives the ionic conductivity figure of low temperature flexibility solid polyelectrolyte film, and test uses occasion China CHI760B
Type electrochemical workstation.
- 20 DEG C of low temperature of the cycle performance figure that Fig. 2 gives solid lithium ion battery passes through the modification system as seen from the figure
Standby solid lithium ion battery shows good low temperature electrochemical performance.
Embodiment 2
The preparation of positive plate:
According to the mass percent of 80:3:7:10, by positive electrode active materials cobalt acid lithium, conductive agent acetylene black, lithium salts lithium perchlorate
It is added in appropriate solvent NMP with binder modification polyvinyl chloride TPE, is tuned into slurry, is coated on aluminium foil after ball milling, so
After be put in baking oven in 80 DEG C of dry 30min, then in vacuum drying oven in 110 DEG C drying obtain positive plate for 24 hours.
The preparation method of low temperature flexibility solid polyelectrolyte film comprises the following steps:
Step S1: modified polyvinyl chloride TPE/ polyvinyl fluoride PVF mixture 2g and lithium salts LiTFSI 0.2g is taken to be dissolved in appropriate solvent
Clarification viscous solution is uniformly mixing to obtain in acetonitrile；
Step S2: being added plasticizer ethylene carbonate EC 0.6g in the viscous solution obtained to step S1, is thoroughly mixed
It is even to obtain solution A；
Step S3: by inorganic particle LLZO 1.2g and tetrahydrofuran mixing and ball milling, mixed system B is obtained after fully dispersed；
Step S4: the mixed system B that step S3 is obtained is added in the solution A that step S2 is obtained, is divided after being sufficiently mixed
Granular media system C；
Step S5: the dispersion C that step S4 is obtained is prolonged into stream film forming in silicone oil paper, is put into vacuum drying oven after natural drying
In 60 DEG C of dry 12h, can from silicone oil paper isolated low temperature flexibility solid polyelectrolyte film.
Comparative example 1
1 difference from Example 1 of comparative example is: without addition modified polyvinyl chloride TPE, the solid-state in solid electrolyte membrane
Dielectric film is unable to normal playback electricity at -20 DEG C.
Fig. 1 gives the ionic conductivity figure of comparative example solid electrolyte film, and test uses occasion China CHI760B type electrochemistry
Work station.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (5)
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