CN103647107A - All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof - Google Patents
All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103647107A CN103647107A CN201310615164.0A CN201310615164A CN103647107A CN 103647107 A CN103647107 A CN 103647107A CN 201310615164 A CN201310615164 A CN 201310615164A CN 103647107 A CN103647107 A CN 103647107A
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- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003792 electrolyte Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 title abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 54
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 28
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 101
- 239000000839 emulsion Substances 0.000 claims description 51
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 45
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 45
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims description 29
- 159000000002 lithium salts Chemical class 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 27
- 238000013019 agitation Methods 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 18
- 229920000126 latex Polymers 0.000 claims description 18
- 239000011256 inorganic filler Substances 0.000 claims description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 17
- 239000000084 colloidal system Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 6
- 239000000052 vinegar Substances 0.000 claims description 6
- 235000021419 vinegar Nutrition 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229940117958 vinyl acetate Drugs 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 210000001124 body fluid Anatomy 0.000 description 4
- 239000010839 body fluid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 241000773945 Trimusculidae Species 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- H01M10/056—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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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- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to an all-solid-state lithium ion battery diaphragm of a microspheric structure and a preparation method thereof, belongs to the technical field of manufacturing of a lithium battery, and aims at providing a solid polymer electrolyte membrane and a modified all-solid-state polymer electrolyte membrane which are used for solving the bottleneck problem of solid polymer electrolyte, i.e. for improving the room-temperature conductivity of the all-solid-state polymer electrolyte. The spherical granularity of the polymer electrolyte membrane and the modified inorganic/organic composite electrolyte membrane is 100nm to 500nm. The prepared all-solid-state polymer electrolyte membrane is good in heat stability and high in room-temperature conductivity and lithium ion transference number. By virtue of the dry-state polymer electrolyte, the phenomenon that an ordinary liquid battery is likely to burn and explode and the like can be avoided, and the safety reliability of the battery can be improved.
Description
Technical field
The present invention relates to solid lithium battery manufacturing technology field, particularly for electrolyte membrance material of the energy storage devices such as lithium (ion) secondary all-solid-state battery and preparation method thereof.
Background technology
Although liquid lithium ionic cell has commercially been obtained very large success, there are several serious deficiencies in it.First, because liquid lithium ionic cell is containing liquid electrolyte, for the packing of shell, relatively limit to; Secondly, the liquid electrolyte that liquid lithium ionic cell is used very easily burns, if battery valve is opened, liquid electrolyte overflows, and the liquid electrolyte of discharge just may burn.This is the potential safety hazard of consumer electronics product maximum; In addition, liquid lithium ionic cell has obvious size restrictions to large-scale and compact battery.
Polymer Li-ion battery is a new direction of lithium-ion technology development, thereby replace liquid electrolyte with polymer dielectric, makes all solid state lithium ion battery.Its major advantage is fundamentally to have solved leakage problem, has further improved fail safe; And shape can change arbitrarily and is easy to make the ultra-thin battery that does not need metal shell packing.Thereby, in polymer Li-ion battery, membrane for polymer electrolyte is being born the role of liquid lithium ionic cell (liquid Li-ion Battery) septation and two kinds of components of electrolyte: it should be kept apart both positive and negative polarity pole piece, make battery internal short-circuit not occur and reduce leakage current (self-discharge phenomenon), for lithium ion transmits and moves between both positive and negative polarity active material, provide path again.Solid polymer lithium ion battery can make up the deficiency of liquid lithium ionic cell.Solid polymer lithium ion battery has material and manufacturing cost is moderate, when abuse safety, without features such as environmental problem and flexible designs.In October, 1997 is made the thinnest (less than 3/4 inch) in the world notebook computer of light (3.1 pounds) by Mitsubishi Electric Corporation, has adopted 1/4 inch of solid polymer lithium ion battery of Ultralife Battery Company.
Core in solid polymer cell is polymer dielectric, but up to now, the applied polymer dielectric of polymer Li-ion battery that really enters the practical production phase is mainly gel polymer electrolyte, as the production method of U.S. Bellcore company at disclosed a kind of polymer Li-ion battery in 1996, be to carry out plastic packaging after the battery of oven dry is flooded in electrolyte.Although the progress of polymer Li-ion battery is very fast, there is finished product battery production in batches, from the domestic and international present Research to polymer Li-ion battery, the performance of existing polymer Li-ion battery is still not ideal enough.Gel-type polymer electrolyte is due to parcel electrolyte thereby still have the Partial security hidden danger as liquid cell, and easily in formation process, occurs inflatable problem, and meanwhile, the defect that this dielectric film is fatal is the bad mechanical strength of film.Thereby although all solid state electrolyte Conductivity Ratio gel-type polymer electrolyte is low, due to its good mechanical strength, high security has incomparable advantage.The low defect of full solid state polymer electrolyte ubiquity room-temperature conductivity of researching and developing at present, great majority are all 10
-5～10
-7s/ cm.The conductivity that how to improve solid-state polymerization dielectric film is taken into account the mechanical strength of film simultaneously, is the important topic in solid lithium ion battery field.Also be the technical barrier urgently to be resolved hurrily of current solid polymer cell commercialized development.Therefore the conductivity, improving every dielectric film is the important leverage that all solid state lithium ion battery applications is achieved.
Summary of the invention
Technical problem to be solved by this invention is in order to improve full solid state polymer electrolyte film room-temperature conductivity, the polymer dielectric film of having prepared a kind of special chondritic, and providing a kind of modification to obtain composite polymeric dielectric film after inorganic nano-filler is multiple, the composite electrolyte membrane of this solid electrolyte membrane and modification is significantly improved than the solid electrolyte membrane room-temperature conductivity that research is reported at present.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
Dielectric film for all solid state lithium ion battery, it is characterized in that: described dielectric film is to be prepared by polymer complex lithium salts, polymer is to consist of polymer microballoon colloidal particle, described polymer microballoon is by acrylonitrile and the vinyl acetate ethyl VEC polymeric colloid that polymerization forms in the organic solution of ethylene-vinyl acetate copolymer EVA, dry except forming the inner dielectric film being comprised of micro-sphere structure after desolventizing, described polyalcohol microspherulite diameter is 100～500nm.
The weight ratio of described ethylene-vinyl acetate copolymer EVA and organic solvent is 1:15-20, and the weight ratio of described acrylonitrile AN and ethylene-vinyl acetate copolymer EVA is 2-8:1, and the mass ratio of described EVA and VEC is 1:2; Dry except forming the inner dielectric film being comprised of micro-sphere structure after desolventizing, described lithium salts accounts for polymer emulsion solid content 5-20%, and described polyalcohol microspherulite diameter is 100～200nm.
Described lithium salts is inorganic anion type, as LiClO
4, LiBF
4, LiPF
6, LiAsF
6; Or organic anion type, as LiCF
3sO
3, LiN (CF
3sO
2)
2(LITFSI), LiC (CF
3sO
2)
3.
Described EVA organic solution organic solvent used is ester class, as ethyl acetate, butyl acetate, vinegar ester ethyl ester, vinegar ester butyl ester, isopropyl acetate etc.; Or ethers is as the mixed solvent with ester class such as Isosorbide-5-Nitrae-dioxane, benzinum, or alcohols is as ethylene glycol, and propylene glycol or isopropyl alcohol equal the mixed solvent of ethers or ester class.
Described polymeric colloid adds nanometer inorganic filler, and its addition is 2～20% of polymeric colloid solid content weight, and the particle diameter of described nanometer inorganic filler is 10～500nm, and described nanometer inorganic filler is Al
2o
3, SiO
2, TiO
2deng.
The addition of described nanometer inorganic filler is 5～10% of polymeric colloid solid content weight, and the particle diameter of described nanometer inorganic filler is 20～100nm.
The preparation method who is used for the dielectric film of all solid state lithium ion battery, is characterized in that: comprise the steps:
A. polymer latex precursor emulsion is synthetic: film forming agent EVA and organic solvent are joined in reaction bulb, add thermal agitation until dissolve completely, add polymerization reaction monomer acrylonitrile AN and vinyl acetate ethyl VEC, mix, then add initator to be warming up to the polymer latex precursor emulsion that 60～80 ℃ of polymerization reaction 8～24h obtain chondritic; By infrared minute water instrument, recording polymeric colloid mass percent in polymer emulsion is 20% left and right.
B. the preparation of polymer dielectric emulsion: electrolyte lithium salt needs predissolve, load weighted lithium salts 2～20% is dissolved in the mixed solution of diethyl carbonate (DEC) or DEC/EC by mass percentage, loose 10 ~ the 60min of excusing from death wavelength-division, stirs 1～6h until be in the polymer latex precursor emulsion that joins a step after clear solution;
C. by polymer emulsion b through casting or the tape casting to PET substrate or polytetrafluoroethylene mould, peel off and obtain polymer electrolyte film after dry.
Initator described in described a step adopts the conventional initator of this area acrylonitrile, and as benzoyl peroxide, azodiisobutyronitrile, the consumption of initator is conventional amount used.
Described b step is: the preparation of polymer dielectric emulsion: electrolyte lithium salt is carried out to predissolve, load weighted lithium salts 5～20% is dissolved in the mixed solution of diethyl carbonate (DEC) or DEC/EC by mass percentage, loose 10 ~ the 60min of excusing from death wavelength-division, joins in polymer latex precursor emulsion and stirs 3～5h until be after clear solution.
In described b step, be also included in polymer dielectric emulsion and add inorganic nano-filler, load weighted inorganic nano-filler is joined in the polymer emulsion that 300g polymeric colloid mass percent is 20%, by Nano filling, account in the mixed solution that 10～60% of polymer latex weight is scattered in diethyl carbonate (DEC) or DEC/EC, employing planetary ball mill disperses, and finely dispersed filler slurry and polymer dielectric solution mechanical agitation mix for 2～8 hours.
Described load weighted inorganic nano-filler 20～40% is scattered in the mixed solution of diethyl carbonate DEC or DEC/EC by mass percentage, employing planetary ball mill disperses, and finely dispersed filler slurry and polymer dielectric solution mechanical agitation mix for 2～8 hours.
The present invention has the following advantages:
1, full solid state polymer electrolyte film of the present invention and modification inorganic/organic composite dielectric film, room-temperature conductivity is higher, than traditional pure solid polymer electrolyte membrane, improve 1 ~ 2 order of magnitude, thereby make all solid state electrolyte film can be applied to become possibility in all-solid-state battery, also substantially solved common all solid state electrolyte face face room-temperature conductivity low bottleneck.Solid electrolyte membrane is applied in all-solid-state battery simultaneously, can avoid the irreversible electrochemical reaction in battery-heating loss of heat process, avoids battery burning, explosion phenomenon to occur, thereby has improved the security reliability of battery; In addition, because polymer microballoon is mainly comprised of the acrylonitrile of strong polarity and the VEC macromolecule that is similar to EC structure, it has good complexing power to electrolyte lithium salt, thereby given dielectric film, has higher room-temperature conductivity and lithium ion transference number.
2, the present invention selects VEC to be because VEC has the following advantages: (1) VEC is flame-retardant additive conventional in electrolyte, has good intermiscibility with electrolyte; (2) VEC structure is similar to the structure of electrolyte common solvent EC, PC, thereby has and be similar to EC, the PC solvability to lithium salts, and polymer dielectric conductivity is improved becomes possibility.(3) in VEC structure, the two keys on straight chain can be participated in copolymerization for it condition is provided.Select EVA to be because EVA has the following advantages: (1) fusing point is low, fusible under lower temperature, reaction; (2) there is good compatibility with other polymer.Select acrylonitrile to be because acrylonitrile is the compound of strong polarity, and its corresponding polyacrylonitrile macromolecule has stronger rigidity, can strengthen the mechanical strength of film.
3, the present invention selects inorganic nano-filler modification to have following advantage: (1) Al
2o
3, SiO
2deng be utilize a large amount of hydroxyl of filling surface can with polymer VEC and EVA in oxygen atom form hydrogen bond, thereby reduce lithium ion and oxygen atom, directly act on, make lithium ion to complete rapidly the process of complexing of complexing-solution complexing-again along polymer segment; (2) interpolation of filler, has increased the specific area of transmitting charge carrier in film, and lithium ion can transmit along nanoparticle surface.
4, accompanying drawing explanation of the present invention
Fig. 1 adds monomer VEC front and back polymer emulsion scanning electron microscope (SEM) photograph: (a) first stage of reaction; (b) second stage.
Fig. 2 is complexing LiCF
3sO
3the scanning electron microscope (SEM) photograph of rear polymer dielectric film.
Fig. 3 is that the conductivity of the polymer dielectric film prepared of four kinds of lithium salts varies with temperature curve chart.
Fig. 4 is that mass fraction is 10% Li (CF
3sO
3)
2the polymer dielectric equivalent circuit diagram of preparation.
Fig. 5 is complexing LiN (CF
3sO
3)
2dielectric film prepared by imines lithium salts is through Al
2o
3each composite electrolyte membrane AC impedance figure and conductivity-temperature profile after modification.
Embodiment
Lithium ion battery provided by the invention is to form by polymer microballoon is tightly packed with full solid state polymer electrolyte film and Nano filling composite electrolyte membrane thereof, and described polymer microballoon is acrylonitrile and vinyl acetate ethyl (VEC) at poly-(ethylene-vinyl acetate) the polymer latex body fluid that (EVA) polymerization forms in copolymer solution.Described polymer latex body fluid is mainly the mixture of acrylonitrile and VEC copolymer, acrylonitrile homopolymer and acrylonitrile grafting EVA product.
Above-mentioned polyalcohol microspherulite diameter is 100～500nm, preferably 100～200nm.
Above-mentioned EVA copolymer solution organic solvent used is ester class, as ethyl acetate, butyl acetate, vinegar ester ethyl ester, vinegar ester butyl ester, isopropyl acetate etc.; Or ethers is as the mixed solvent with ester class such as Isosorbide-5-Nitrae-dioxane, benzinum, or alcohols is as ethylene glycol, and propylene glycol or isopropyl alcohol equal the mixed solvent of ethers or ester class.
Further, in above-mentioned polymer dielectric colloid emulsion, also can add nanometer inorganic filler, form the full solid state polymer electrolyte film of inorganic/organic composite.
Wherein, nanometer inorganic filler is Al
2o
3, SiO
2, TiO
2deng, addition is 2～20 wt.% (with polymeric colloid solid content weighing scales), preferably 5～10 wt.%; Described nanometer inorganic filler particle diameter is 10～500 nm, preferably 20～100 nm.Nanometer inorganic filler addition too much can affect the integrality of sphere structure in the film forming of polymer and film, very few not obvious to improving the mechanical strength of film and improving conductivity.
The all solid state polyelectrolyte membranes of the present invention and modification inorganic/preparation method of organic composite dielectric film, concrete grammar is as follows:
The preparation of a, polymer dielectric colloid emulsion
First EVA is dissolved in organic solvent, adds acrylonitrile monemer in this EVA solution and be warming up to 70～80 ℃; Then be added dropwise to the solution polymerization 2～5 hours that contains initator benzoyl peroxide, add the further polymerization of VEC after 6～24 hours polymer latex body fluid.Appropriate lithium salts ultrasonic dissolution, in the mixed solution of diethyl carbonate (DEC) or DEC/EC, is joined consoluet lithium salt solution in polymer latex precursor emulsion, to stir 1～6 h.
The preparation of the composite polymer electrolyte emulsion of b, inorganic nano-filler modification
Step a resulting polymers colloidal solution is mixed 2～8 hours with the polymer latex body fluid mechanical agitation of the finely dispersed nanometer inorganic filler of ball milling, obtain modification inorganic/organic composite electrolyte emulsion.
C, by the polymer emulsion after electrolytic polymer emulsion or modification through casting or the tape casting to PET substrate or polytetrafluoroethylene mould, peel off and obtain polymer electrolyte film after dry.
Mode by specific embodiment is further described the present invention below.
embodiment 1
In tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 93.6 g acrylonitrile (AN) monomers, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 46.8g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, solid content is 20 wt.% left and right, described polyalcohol microspherulite diameter is 100～500nm, latex particle size size is controlled by polymeric reaction condition, gained colloid emulsion particle diameter records through Ma Erwen laser particle analyzer, to reaction system, add the size variation of former and later two stage colloidal particle particle diameters of VEC to carry out comparative analysis from scanning electron microscope (SEM) photograph, as shown in Figure 1, as can be seen from the figure, second step adds after monomer VEC, and it is large that polymer spheres particle diameter becomes.
Get the polymer emulsion of 100 g in above-mentioned, add the lithium perchlorate (LiClO that the 20g mass percent of ultrasonic dissolution is 10wt.% in advance
4) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiClO
4electrolyte solution, the tape casting or pour into dielectric film.Dry after moisture, peeling off and obtaining thickness is the full solid state polymer electrolyte film that 20～40 μ m are thick.
embodiment 2
In tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 187.2g acrylonitrile (AN) monomer, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 50.4g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, solid content is 20 wt.% left and right, described polyalcohol microspherulite diameter is 100～200nm, latex particle size size is controlled by polymeric reaction condition, gained colloid emulsion particle diameter records through Ma Erwen laser particle analyzer, to reaction system, add the size variation of former and later two stage colloidal particle particle diameters of VEC to carry out comparative analysis from scanning electron microscope (SEM) photograph, as shown in Figure 1, as can be seen from the figure, second step adds after monomer VEC, and it is large that polymer spheres particle diameter becomes.
Get the polymer emulsion of 100 g in above-mentioned, add the LiBF4 (LiBF that the 20g mass percent of ultrasonic dissolution is 10wt.% in advance
4) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiBF
4electrolyte solution, the tape casting or pour into dielectric film.Dry after moisture, peeling off and obtaining thickness is the full solid state polymer electrolyte film that 20～40 μ m are thick.
embodiment 3
In tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 46.8 g acrylonitrile (AN) monomers, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 50.4g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, solid content is 20 wt.% left and right, and described polyalcohol microspherulite diameter is 300nm, and latex particle size size is controlled by polymeric reaction condition, gained colloid emulsion particle diameter records through Ma Erwen laser particle analyzer, to reaction system, add the size variation of former and later two stage colloidal particle particle diameters of VEC to carry out comparative analysis from scanning electron microscope (SEM) photograph, as shown in Figure 1, as can be seen from the figure, second step adds after monomer VEC, and it is large that polymer spheres particle diameter becomes.
Get the polymer emulsion of 100 g in above-mentioned, add the trifluoro first class Sulfonic Lithium (LiCF that 15 g mass percents of ultrasonic dissolution are 15wt.% in advance
3sO
3) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiCF
3sO
3electrolyte solution, the tape casting or pour into dielectric film.Dry after moisture, peeling off and obtaining thickness is the full solid state polymer electrolyte film that 20～40 μ m are thick, as shown in Figure 2, and complexing LiCF
3sO
3the scanning electron microscope (SEM) photograph of rear polymer dielectric film.
embodiment 4
In tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 70.2 g acrylonitrile (AN) monomers, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 50.4g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, and solid content is 20 wt.% left and right.
Get the upper polymer emulsion of 100 g, add two trifluoro first class sulfimide lithium (LiN (CF that 12 g mass percents of ultrasonic dissolution are 18wt.% in advance
3sO
3)
2) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiN (CF
3sO
3)
2electrolyte solution, the tape casting or pour into dielectric film.Dry after moisture, peeling off and obtaining thickness is the full solid state polymer electrolyte film that 20～40 μ m are thick.Electrolyte Electronic Speculum pattern as shown in Figure 2, can find out, when lithium salt is 10 wt.%, the surface of prepared dielectric film is comprised of the spherical particle of regular homogeneous.
1. in tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 93.6 g acrylonitrile (AN) monomers, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 50.4g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, and solid content is 20 wt.% left and right.
2. get the upper polymer emulsion of 100 g, add two trifluoro first class sulfimide lithium (LiN (CF that 12 g mass percents of ultrasonic dissolution are 18wt.% in advance
3sO
3)
2) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiN (CF
3sO
3)
2electrolyte solution.
3. by load weighted nanometer inorganic filler Al
2o
3particle diameter is 10～500nm, 40g 20% is scattered in the mixed solution of 55g diethyl carbonate (DEC) or DEC/EC by mass percentage, and add 5g PVDF adhesive, planetary ball mill is dispersed into filler slurry dispersion liquid, and rotational speed of ball-mill is controlled at 200～400 hr Ball-milling Time approximately 2～8 hours.
4. respectively get the 2. polymer dielectric solution of 5 parts of 20g in step, by the 3. the filler slurry dispersion liquid in step add in aforementioned polymer electrolyte solution, mechanical agitation mixes for 2～8 hours, gained slurry through casting method or in PET substrate curtain coating prepare filer content be 2～10wt.% a series of inorganic/organic composite solid dielectric film.
embodiment 6
1. in tri-mouthfuls of round-bottomed flasks of the 1L with reflux condensing tube and blender, add ethyl acetate and 1, organic mixed solvent of 4-dioxane (400 g) and 23.4 g ethylene-vinyl acetate copolymer (EVA, Sumitate KC-10,28wt% vinylacetate), mixture is heated to 70 ℃ and be dissolved in solvent completely under mechanical agitation, and then dropwise splash into 93.6 g acrylonitrile (AN) monomers, pass into nitrogen after 30 minutes, then the 30 mL toluene solutions that are dissolved with 0.49 g benzoyl peroxide are slowly dropped in reaction system.Dropwise rear reaction approximately 1 hour, question response thing dropwise adds vinyl acetate ethyl (VEC, 50.4g) after being transformed into micro-yellow emulsion form again, reacts after 8 hours, obtains P(AN
-co-vEC)/EVA polymer emulsion.In this reaction system, the conversion ratio of AN is more than 85%, and solid content is 20 wt.% left and right.
2. get the upper polymer emulsion of 100 g, add two trifluoro first class sulfimide lithium (LiN (CF that 12 g mass percents of ultrasonic dissolution are 18wt.% in advance
3sO
3)
2) solution, 50 ℃ of mechanical agitation obtain lithium salt content (with respect to polymer weight) about 2～6 hours be the P(AN of 10 wt.%
-co-vEC)/EVA-LiN (CF
3sO
3)
2electrolyte solution.
3. by load weighted nanometer inorganic filler SiO
2particle diameter is that 20～100nm 40g 20% is scattered in the mixed solution of 55g diethyl carbonate (DEC) or DEC/EC by mass percentage, and add 5g PVDF adhesive, planetary ball mill is dispersed into filler slurry dispersion liquid, and rotational speed of ball-mill is controlled at 300～400 hr Ball-milling Time approximately 4～6 hours.
4. respectively get the 2. polymer dielectric solution of 5 parts of 20g in step, by the 3. the filler slurry dispersion liquid in step add in aforementioned polymer electrolyte solution, mechanical agitation mixes for 2～8 hours, gained slurry through casting method or in PET substrate curtain coating prepare filer content be 2～10wt.% a series of inorganic/organic composite solid dielectric film.
test example 1
Four kinds of dielectric films corresponding to different lithium salt that embodiment 2～4 is made are clipped between the stainless steel electrode of two polishings, are encapsulated in 2032 button shells, for electrode is fully contacted with SPE, add stainless steel spring sheet in housing.At a certain temperature, adopt electrochemical impedance instrument (Solartron 1260+1287, Zplot software) record dielectric film volume resistance (
r b), and calculate the conductivity under dielectric film corresponding temperature through correlation formula, and test result is listed in table 1, and corresponding equivalent electric circuit and conductivity-temperature profile are as shown in Figure 3, Figure 4.
Polymer dielectric film room-temperature conductivity value contrast prepared by four kinds of lithium salts of table 1
Note: in table
dwith
sbe respectively the thickness (cm) of polymer dielectric film and the effective area (cm of test electrode
2)
test example 2
The dielectric film of embodiment 4 preparations is clipped between two fresh lithium metals, is encapsulated in 2032 button shells, for electrode is fully contacted with SPE, in housing, add stainless steel steel disc and spring leaf.The technology that adopts direct current polarization and AC impedance to combine, measures the lithium ion transference number of this serial SR polymer dielectric.First from direct current polarization curve, analyze i
0and is, from impedance spectrum, analyze interface resistance R
0and Rs, then use conventional lithium ion transference number formula (2-1) to calculate polymer dielectric film lithium ion transference number prepared by different lithium salinity and be listed in table 2.
test example 3
Modified inorganic/organic composite dielectric film salt of the different filer contents that embodiment 5 and example 6 are made is clipped between the stainless steel electrode of two polishings, be encapsulated in 2032 button shells, for electrode is fully contacted with SPE, in housing, add stainless steel spring sheet.At a certain temperature, adopt electrochemical impedance instrument (Solartron 1260+1287, Zplot software) record dielectric film volume resistance (
r b), computing formula is 1 identical with test, calculates the conductivity of dielectric film room temperature to 70 ℃, according to conductivity value, draws relevant conductivity-temperature profile, and the AC impedance that it is corresponding and conductivity-temperature profile are as shown in Figure 5.From figure, can contrast and find out, the dielectric film conductivity value after filler modified is better than the pure solid polymer electrolyte conductivity value before modification, and the interpolation of filler exists optimum value.
Claims (10)
1. for the dielectric film of all solid state lithium ion battery, it is characterized in that: described dielectric film is to be prepared by polymer complex lithium salts, polymer is to consist of polymer microballoon colloidal particle, described polymer microballoon is by acrylonitrile and the vinyl acetate ethyl VEC polymeric colloid that combined polymerization forms in the organic solution of ethylene-vinyl acetate copolymer EVA, dry except forming the inner dielectric film being comprised of micro-sphere structure after desolventizing, described polyalcohol microspherulite diameter is 100～500nm.
2. the dielectric film for all solid state lithium ion battery according to claim 1, it is characterized in that: the mass ratio of described EVA and VEC is 1:2, the weight ratio of described ethylene-vinyl acetate copolymer EVA and organic solvent is 1:15-20, the weight ratio of described acrylonitrile AN and ethylene-vinyl acetate copolymer EVA is 2-8:1, described lithium salts accounts for polymer emulsion solid content 5-20%, and described polyalcohol microspherulite diameter is 100～200nm.
3. the dielectric film for all solid state lithium ion battery according to claim 1, is characterized in that: described lithium salts is inorganic anion type, as LiClO
4, LiBF
4, LiPF
6, LiAsF
6; Or organic anion type, as LiCF
3sO
3, LiN (CF
3sO
2)
2(LITFSI), LiC (CF
3sO
2)
3.
4. the dielectric film for all solid state lithium ion battery according to claim 1, is characterized in that: described EVA organic solution organic solvent used is ester class, as ethyl acetate, butyl acetate, vinegar ester ethyl ester, vinegar ester butyl ester, isopropyl acetate etc.; Or ethers is as the mixed solvent with ester class such as Isosorbide-5-Nitrae-dioxane, benzinum, or alcohols is as ethylene glycol, and propylene glycol or isopropyl alcohol equal the mixed solvent of ethers or ester class.
5. the dielectric film for all solid state lithium ion battery according to claim 1, it is characterized in that: described polymeric colloid adds nanometer inorganic filler, its addition is 2～20% of polymer emulsion solid content weight, the particle diameter of described nanometer inorganic filler is 10～500nm, and described nanometer inorganic filler is Al
2o
3, SiO
2, TiO
2.
6. the dielectric film for all solid state lithium ion battery according to claim 5, is characterized in that: the addition of described nanometer inorganic filler is 5～10% of polymer emulsion solid content weight, and the particle diameter of described nanometer inorganic filler is 20～100nm.
7. according to the preparation method of the arbitrary described dielectric film for all solid state lithium ion battery of claim 1-6, it is characterized in that: comprise the steps:
A. polymer latex precursor emulsion is synthetic: film forming agent EVA and organic solvent are joined in reaction bulb, add thermal agitation until dissolve completely, add polymerization reaction monomer acrylonitrile AN and vinyl acetate ethyl VEC, mix, then add initator to be warming up to the polymer latex precursor emulsion that 60～80 ℃ of polymerization reaction 8～24h obtain chondritic;
B. the preparation of polymer dielectric emulsion: electrolyte lithium salt needs predissolve, described lithium salts 2～30% is dissolved in the mixed solution of diethyl carbonate (DEC) or DEC/EC by mass percentage, loose 10 ~ the 60min of excusing from death wavelength-division, stirs 1～6h until be in the polymer latex precursor emulsion that joins a step after clear solution;
C. by polymer emulsion b through casting or the tape casting to PET substrate or polytetrafluoroethylene mould, peel off and obtain polymer electrolyte film after dry.
8. the preparation method of the dielectric film for all solid state lithium ion battery according to claim 7, is characterized in that:
Initator described in a step adopts the conventional initator of this area acrylonitrile, and as benzoyl peroxide, azodiisobutyronitrile, the consumption of initator is conventional amount used.
9. the preparation method of the dielectric film for all solid state lithium ion battery according to claim 7, it is characterized in that: described b step is: the preparation of polymer dielectric emulsion: electrolyte lithium salt is carried out to predissolve, described lithium salts 5～20% is dissolved in the mixed solution of diethyl carbonate (DEC) or DEC/EC by mass percentage, loose 10 ~ the 60min of excusing from death wavelength-division, joins in polymer latex precursor emulsion and stirs 3～5h until be after clear solution.
10. according to the preparation method of the dielectric film for all solid state lithium ion battery described in claim 7 or 8 or 9, it is characterized in that: in described b step, be also included in polymer dielectric emulsion and add inorganic nano-filler, described inorganic nano-filler is scattered in the mixed solution of diethyl carbonate (DEC) or DEC/EC by 10～60% of polymer latex weight, employing planetary ball mill disperses, and finely dispersed filler slurry and polymer dielectric solution mechanical agitation mix for 2～8 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002280072A (en) * | 2001-03-19 | 2002-09-27 | National Institute Of Advanced Industrial & Technology | Battery incorporating organic/inorganic composite polymer solid electrolyte |
| CN102208680A (en) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | Gel electrolyte and preparation method thereof and corresponding anode and lithium sulfur battery |
| KR101176749B1 (en) * | 2011-03-14 | 2012-08-23 | 현대중공업 주식회사 | Solid electrolyte membrane for lithium secondary battery using porous inorganic matter and manufacturing method thereof |
| CN102709597A (en) * | 2012-06-01 | 2012-10-03 | 中国东方电气集团有限公司 | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery |
-
2013
- 2013-11-28 CN CN201310615164.0A patent/CN103647107B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002280072A (en) * | 2001-03-19 | 2002-09-27 | National Institute Of Advanced Industrial & Technology | Battery incorporating organic/inorganic composite polymer solid electrolyte |
| KR101176749B1 (en) * | 2011-03-14 | 2012-08-23 | 현대중공업 주식회사 | Solid electrolyte membrane for lithium secondary battery using porous inorganic matter and manufacturing method thereof |
| CN102208680A (en) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | Gel electrolyte and preparation method thereof and corresponding anode and lithium sulfur battery |
| CN102709597A (en) * | 2012-06-01 | 2012-10-03 | 中国东方电气集团有限公司 | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| G.FEUILLADE ETAL: ""ion-conductive macromoleular gels and membranes for solid lithium cells"", 《JOURNAL OF APPLIED ELECTROCHEMISTY》, vol. 5, no. 1, 1 February 1975 (1975-02-01), pages 63 - 69, XP001007147, DOI: doi:10.1007/BF00625960 * |
| 付延鲍 等: "锂及锂离子蓄电池聚合物电解质研究进展", 《电源技术》, vol. 26, no. 1, 28 February 2002 (2002-02-28), pages 47 - 55 * |
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| US11271214B2 (en) | 2015-12-02 | 2022-03-08 | California Institute Of Technology | Three-dimensional ion transport networks and current collectors for electrochemical cells |
| US11894562B2 (en) | 2015-12-02 | 2024-02-06 | California Institute Of Technology | Three-dimensional ion transport networks and current collectors for electrochemical cells |
| CN109690862A (en) * | 2016-09-13 | 2019-04-26 | 新加坡国立大学 | Solid electrolyte |
| WO2018052371A1 (en) * | 2016-09-13 | 2018-03-22 | National University Of Singapore | Solid electrolyte |
| JP2019526893A (en) * | 2016-09-13 | 2019-09-19 | ナショナル ユニバーシティー オブ シンガポールＮａｔｉｏｎａｌ Ｕｎｉｖｅｒｓｉｔｙ ｏｆ Ｓｉｎｇａｐｏｒｅ | Solid electrolyte |
| US11133527B2 (en) | 2016-09-13 | 2021-09-28 | National University Of Singapore | Solid electrolyte |
| CN107134587B (en) * | 2017-04-26 | 2019-06-18 | 华中科技大学 | A kind of solid electrolyte inorganic nano particle filler and preparation method thereof |
| CN107134587A (en) * | 2017-04-26 | 2017-09-05 | 华中科技大学 | A kind of solid electrolyte inorganic nano particle filler and preparation method thereof |
| CN107069085B (en) * | 2017-05-04 | 2019-12-03 | 中国科学院化学研究所 | A kind of flexible solid method for preparing polymer electrolytes and application |
| CN107069085A (en) * | 2017-05-04 | 2017-08-18 | 中国科学院化学研究所 | One class flexible solid method for preparing polymer electrolytes and application |
| CN107346833B (en) * | 2017-08-30 | 2020-03-31 | 清陶（昆山）能源发展有限公司 | Composite solid polymer electrolyte film and preparation method thereof |
| CN107346833A (en) * | 2017-08-30 | 2017-11-14 | 清陶（昆山）能源发展有限公司 | A kind of composite solid polymer electrolyte film and preparation method thereof |
| CN108550906A (en) * | 2018-04-24 | 2018-09-18 | 珠海光宇电池有限公司 | A kind of preparation method of compound all-solid polymer electrolyte film |
| CN109802174A (en) * | 2019-01-10 | 2019-05-24 | 北京工业大学 | A kind of preparation and its application of polycarbonate base polymer electrolyte |
| CN114335699A (en) * | 2021-12-31 | 2022-04-12 | 重庆长安新能源汽车科技有限公司 | Core-shell structure composite solid electrolyte and preparation method thereof |
| CN115020796A (en) * | 2022-07-11 | 2022-09-06 | 天津工业大学 | Microsphere electrolyte, preparation method and application thereof, yarn-shaped flexible battery and preparation method thereof |
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Effective date of registration: 20180426 Address after: 610000 18 West core road, hi-tech West District, Chengdu, Sichuan Patentee after: Dongfang Electric Co., Ltd. Address before: 610036 Shu Han Road, Jinniu District, Chengdu, Sichuan Province, No. 333 Patentee before: Dongfang Electric Corporation |