CN110048155A - A kind of solid electrolyte and preparation method thereof and lithium ion battery - Google Patents
A kind of solid electrolyte and preparation method thereof and lithium ion battery Download PDFInfo
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- CN110048155A CN110048155A CN201910368200.5A CN201910368200A CN110048155A CN 110048155 A CN110048155 A CN 110048155A CN 201910368200 A CN201910368200 A CN 201910368200A CN 110048155 A CN110048155 A CN 110048155A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 133
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000011159 matrix material Substances 0.000 claims abstract description 71
- 239000011256 inorganic filler Substances 0.000 claims abstract description 43
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 43
- -1 alkali metal salt Chemical class 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 41
- 229910003002 lithium salt Inorganic materials 0.000 claims description 31
- 159000000002 lithium salts Chemical group 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002145 thermally induced phase separation Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000010146 3D printing Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 229910012464 LiTaF6 Inorganic materials 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 3
- 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 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002365 multiple layer Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 11
- 229910003480 inorganic solid Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 239000005518 polymer electrolyte Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000011165 3D composite Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000013259 porous coordination polymer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 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
- H01M10/052—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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of solid electrolyte and preparation method thereof and lithium ion batteries.The solid electrolyte includes porous polymer matrix, the inorganic filler in the porous polymer matrix hole, and the modifier on the porous polymer matrix surface, the modifier include polymer dielectric and alkali metal salt.The preparation method includes: (1) substrate that in the gap of inorganic filler filling porous polymer matrix, will obtain that treated；(2) polymer dielectric and alkali metal salt are assembled in step (1) treated the substrate surface, obtain the solid electrolyte.Solid electrolyte provided by the invention has high ionic conductivity and high mechanical strength simultaneously.
Description
Technical field
The invention belongs to battery technology field, it is related to a kind of electrolyte and preparation method thereof more particularly to a kind of solid-state electricity
Solve matter and preparation method thereof and lithium ion battery.
Background technique
High-performance, safe and economic energy storage mode are pursuing a goal for current many fields, and people will wish
Place on the secondary lithium battery and new material of rapid development.With to lithium ion battery security and high-energy density requirement
Continuous promotion, sight is increasingly turned to all-solid lithium-ion battery by people.Traditional liquid electrolyte is replaced with solid electrolyte
It is the fundamental way for obtaining the all-solid lithium-ion battery of high-energy density, safety and long circulation life.
Solid electrolyte includes colloidal polymer electrolyte, full solid state polymer electrolyte and inorganic solid electrolyte.
Colloidal polymer electrolyte still contains a large amount of liquid solvents, can not thoroughly solve the safety issue of battery；Full solid state polymer
Electrolyte is usually complexed by polarity macromolecule and metal salt, because its with high safety, mechanical flexibility, viscoelasticity, easily
Film forming, reconfigurable, light specific gravity, it is at low cost many advantages, such as, it is considered to be next-generation high energy memory device is with most potential
One of electrolyte.But solid polyelectrolyte conductivity at room temperature several orders of magnitude low compared with conventional liquid electrolyte, sternly
Its application in lithium ion battery is affected again.Simultaneously at the same time, polymer dielectric has better flexibility and can
There is relatively good contact interface between processability, with electrode, but the conductivity at room temperature of polymer dielectric is lower,
Generally require be higher than its melt temperature more than at a temperature of work, as polyethylene glycol oxide (PEO) base electrolyte generally requires
It could work at a temperature of higher than 60 DEG C or more.Although the polymer dielectric ion-conductance with higher when being higher than melt temperature
Conductance, but thawing or amorphous state is presented in polymer at this time, the mechanical property of polymer dielectric reduces, and lower than thawing
Although polymer mechanical strength with higher when temperature, ionic conductivity at this time is again lower, is not able to satisfy normal work
The requirement of work.Therefore urgent problem is the lance between high ionic conductivity and high mechanical strength in polymer dielectric
Shield.
CN109148945A discloses a kind of three-dimensional composite solid electrolyte and preparation method thereof of structure-controllable, this method
In, three-dimensional composite solid electrolyte is made of inorganic solid electrolyte skeleton, polymer dielectric and lithium salts, inorganic solid-state electrolysis
The mass ratio of matter skeleton, polymer dielectric and lithium salts is 0.15~0.85:0.15~0.85:0.05~0.15.The program
Using inorganic solid electrolyte as skeleton, it is unfavorable for improving the maximum stress of electrolyte.
CN109301320A discloses composite solid electrolyte and the preparation side of a kind of inorganic solid electrolyte vertical orientation
Method belongs to lithium ion battery solid electrolyte technical field.Composite solid electrolyte is by inorganic solid electrolyte, polymer electrolytic
Matter and lithium salts composition, the mass ratio of inorganic solid electrolyte, polymer dielectric and lithium salts is 0.1~0.9:0.1~0.9:
0.03~0.5.The program prepares inorganic solid electrolyte nanofiber by electrostatic spinning, and it is passed through electric field orientation legal system
Standby vertically oriented inorganic solid electrolyte skeleton, is poured to form composite solid electrolyte with polymer and lithium salts.The program is adopted
It uses inorganic solid electrolyte as skeleton, is unfavorable for improving the maximum stress of electrolyte.
CN105826602A discloses a kind of lithium-sulfur cell all solid state electrolyte and preparation method thereof, is electrolysed described in this method
Lithium salts is distributed in matrix porosity using aluminium Porous coordination polymer as skeleton in matter.The preparation are as follows: by aluminium Porous coordination polymer
It is added to leaching in the organic solution of lithium salts to set, be dried in vacuo, then leaching is placed in lithium-sulfur cell electrolyte, in inert gas flow
Lower drying, vacuum drying, obtains the electrolyte.The application range of the program is very narrow, is only limitted to lithium-sulfur cell, and mechanics
Performance and electric conductivity need to be further increased.
Summary of the invention
Not for the problem that polymer dielectric High Temperature ionic Conductivity of the existing technology is high but its mechanical property is low
Foot, it is provided by the invention solid the purpose of the present invention is to provide a kind of solid electrolyte and preparation method thereof and lithium ion battery
State electrolyte is meeting high temperature Li+Quick transmission path while, have higher mechanical strength.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of solid electrolyte, the solid electrolyte includes porous polymer matrix, position
Inorganic filler in the porous polymer matrix hole, and the modification on the porous polymer matrix surface
Object, the modifier include polymer dielectric and alkali metal salt.
Solid electrolyte provided by the invention is a kind of organic bath of three-dimensional framework Auxiliary support, at the same have it is high from
Electron conductivity and high mechanical strength, being able to solve the generally existing ionic conductivity of solid electrolyte and mechanical strength cannot be considered in terms of
The problem of.There is porous polymer matrix to play skeleton function in solid electrolyte provided by the invention, facilitates solid state electrolysis
Matter large area film forming, is particularly suitable for preparing the battery core of winding process type.Nothing is only leaned on if not using porous polymer matrix
Machine object is then only used for small-sized lamination process as skeleton, for the battery core of winding process type, it may appear that large area ceramics are viscous
The problem of connecing loosely with removing.
In the present invention, porous polymer matrix plays skeleton function, and the work for promoting heat resistance and rigidity is played in inorganic filler
With.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the porous polymer matrix include polyethylene substrate, polypropylene base,
Any one in polyethylene/polypropylene/polyethylene substrate, polypropylene/polypropylene/polypropylene base or non-woven fabrics or at least two
The combination of kind.It is typical but be non-limiting combination and have: the combination of polyethylene substrate and polypropylene base, polyethylene substrate and nothing
The combination of woven fabric, polyethylene/polypropylene/polyethylene substrate and the combination of polypropylene/polypropylene/polypropylene base etc..
Preferably, the porosity of the porous polymer matrix be 50~70%, such as 50%, 55%, 60%, 65% or
70% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.The present invention
In, if the porosity of porous polymer matrix is excessive, the mechanical strength that will lead to substrate is reduced, and inorganic filler can not be filled in
In the hole of polymeric substrate；If the porosity of porous polymer matrix is too small, polymer dielectric layering will lead to, it can not
The polymer dielectric of connection between layers.
Preferably, the porous polymer matrix is membranaceous.
Preferably, the porous polymer matrix with a thickness of 5~25 μm, such as 5 μm, 10 μm, 15 μm, 20 μm or 25 μm
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.In the present invention, such as
The thickness of fruit porous polymer matrix is excessive, will lead to the overlong time of dipping, increases the time of operation；If porous polymer
The thickness of substrate is too small, will lead in the hole that partial filler can not be filled in inside polymeric substrate.Here, described porous poly-
The thickness for closing object substrate refers to the thickness of single substrate film.
Preferably, in the solid electrolyte, porous polymer matrix multiple-layer stacked is repaired containing described between layers
Jewelry.
Preferably, the modifier is also located in poromeric gap.
Preferably, the number of plies of the porous polymer matrix is 4~6 layers, such as 4 layers, 5 layers or 6 layers.
Preferably, the surface density of the porous polymer matrix is 2.2~13.0g/m2.Such as 2.2g/m2、4.4g/m2、
6.6g/m2、8.8g/m2Or 11.0g/m2Deng it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.Wherein the substrate surface density of 5 μ m thicks is 2.2-2.6g/m2, the substrate surface density of 10 μ m thicks is 4.4-
5.2g/m2, the substrate surface density of 15 μ m thicks is 6.6-7.8g/m2, the substrate surface density of 20 μ m thicks is 8.8-10.4g/m2,
The substrate surface density of 25 μ m thicks is 11.0-13.0g/m2。
In the present invention, if the surface density of the porous polymer matrix is excessive, it is too small to will lead to porosity, will lead to poly-
Polymer electrolyte layering, can not the polymer dielectric of connection between layers；If surface density is too small, the machine of substrate will lead to
Tool strength reduction, inorganic filler can not be also filled in the hole of polymeric substrate.
Preferably, the solid electrolyte is membranaceous, with a thickness of 80~130 μm, such as 80 μm, 90 μm, 100 μm, 110
μm, 120 μm or 130 μm etc., it is not limited to cited numerical value, other unlisted numerical value are equally suitable in the numberical range
With.
As currently preferred technical solution, the inorganic filler includes magnesia, zirconium oxide, calcium carbonate, titanium dioxide
In silicon, aluminum oxide, boehmite, titanium dioxide, barium sulfate, calcium sulfate, attapulgite or zeolite any one or at least
Two kinds of combination.It is typical but be non-limiting combination and have: the group of the combination of magnesia and zirconium oxide, calcium carbonate and silica
It closes, the combination of aluminum oxide and boehmite, titanium dioxide and the combination of barium sulfate etc..It is not limited to the nothing of mentioned kind
Machine filler, other inorganic fillers that can play phase same-action can also be used for the present invention, such as Li1+xAlxGe2-x(PO4)3/
Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2- nNbnO12、Li7-2nLa3Zr2-nWnO12、Li7-2nLa3Zr2-nTenO12、Li7-3nGenLa3Zr2O12And Li7-3nAlnLa3Zr2O12In
Any one or at least two combination.
As currently preferred technical solution, the polymer dielectric includes polyethylene glycol oxide, polyacrylonitrile, poly- first
It is any in base methyl acrylate, Kynoar, polycarbonate, Kynoar-hexafluoropropene or dimethyl silicone polymer
It is a kind of or at least two combination.It is typical but be non-limiting combination and have: the combination of polyethylene glycol oxide and polyacrylonitrile, poly- first
The combination of base methyl acrylate and Kynoar, Kynoar-hexafluoropropene and the combination of dimethyl silicone polymer etc..
Preferably, the alkali metal salt is lithium salts.
Preferably, the lithium salts includes LiClO4、LiPF6、LiAsF6、LiBF4、LiAlCl4、LiSCN、LiTaF6、
LiSnF6、LiGeF6、LiCF3SO3、LiN(SO2CF3)2In LiTFSI any one or at least two combination.It is typical but
Being non-limiting combination has: LiClO4And LiPF6Combination, LiAsF6And LiBF4Combination, LiAlCl4With the group of LiSCN
It closes, LiTaF6And LiSnF6Combination etc..Wherein LiTFSI refers to bis- (fluoroform sulphonyl) imine lithiums.
As currently preferred technical solution, in the solid electrolyte, inorganic filler, polymer dielectric and lithium salts
Mass ratio be (0.02~0.75): (0.15~0.85): (0.15~0.85): (0.05~0.15), such as 0.02:0.15:
0.85:0.05,0.75:0.85:0.15:0.15,0.3:0.6:0.3:0.1 or 0.5:0.4:0.6:0.1 etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Second aspect, the present invention provide a kind of preparation method of solid electrolyte as described in relation to the first aspect, the method packet
Include following steps:
(1) substrate that in the gap of inorganic filler filling porous polymer matrix, will obtain that treated；
(2) polymer dielectric and alkali metal salt are assembled in step (1) treated the substrate surface, obtained described
Solid electrolyte.
As currently preferred technical solution, step (1) sky by inorganic filler filling porous polymer matrix
Method in gap obtains the first mixed liquor, by porous polymer matrix the following steps are included: inorganic filler is mixed with the first solvent
Material is soaked in first mixed liquor, separation of solid and liquid obtains that treated substrate.
It is to be filled up completely inorganic filler in the porous polymer as solid electrolyte skeleton using the purpose of immersion
In the pore structure of substrate.
Preferably, first solvent includes any in dimethylformamide, ethyl alcohol, acetone, tetrahydrofuran or acetonitrile
It is a kind of or at least two combination.It is typical but be non-limiting combination and have: the combination of dimethylformamide and ethyl alcohol, ethyl alcohol and
The combination etc. of the combination of acetone, tetrahydrofuran and acetonitrile.
Preferably, in first mixed liquor, the mass concentration of inorganic filler is 0.1~10.0g/L, such as 0.1g/L,
0.5g/L, 1g/L, 2g/L, 5g/L, 7g/L, 8g/L or 10g/L etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable.
Preferably, the temperature of the immersion is 15~35 DEG C.
Preferably, the time of the immersion is 10~30min, such as 10min, 15min, 20min, 25min or 30min
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the preparation method of step (1) described porous polymer matrix include thermally induced phase separation, dry method list draw,
Any one in the double drawings of dry method, three-layer co-extruded, freezing casting, electrostatic spinning, foaming agent foam or 3D printing or at least two
Combination.The above method can hole size, porosity, the degree of order etc. to porous polymer matrix preferably regulated and controled.
As currently preferred technical solution, step (2) is described to be assembled in step for polymer dielectric and alkali metal salt
Suddenly (1) described treated substrate surface method the following steps are included:
(2 ') mix polymer dielectric, alkali metal salt and the second solvent, obtain the second mixed liquor；
Step (2 ') second mixed liquor is cast in the surface of step (1) treated the substrate by (2 "), dry
After obtain the solid electrolyte.
Preferably, in step (2 ') second mixed liquor, the mass concentration of polymer dielectric is 0.5~10.0g/L,
Such as 0.5g/L, 1g/L, 2g/L, 5g/L, 8g/L or 10g/L etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.
Preferably, in step (2 '), second solvent includes dimethylformamide, ethyl alcohol, acetone, tetrahydrofuran or second
In nitrile any one or at least two combination.It is typical but be non-limiting combination and have: dimethylformamide and ethyl alcohol
Combination, the combination of ethyl alcohol and acetone, tetrahydrofuran and the combination of acetonitrile etc..
Preferably, in step (2 "), second mixed liquor is divided 3~4 times and is poured, such as 3 times, 4 times or 5 times.
Preferably, in step (2 "), further includes: after the casting, repeat step (3) described casting, and every time
Upper step (1) treated the substrate is relay before repeating in last time casting rear substrate.It is above-mentioned to repeat to grasp in the present invention
The purpose of work is, can the three-dimensional structure to solid electrolyte preferably controlled, being more advantageous to keeps solid electrolyte simultaneous
Have ionic conductivity and mechanical strength, facilitates the fracture energy for promoting solid electrolyte, while solid-state can be prepared with large area
Dielectric film improves the processing service performance of solid electrolyte.
Preferably, the duplicate number is 3~5 times, such as 3 times, 4 times or 5 times.Duplicate purpose is to make solid
State electrolyte reaches required thickness.
Preferably, in step (2 "), the method for the drying is that vacuum drying and/or glove box are dry.
Preferably, in step (2 "), the temperature of the drying is 0~80 DEG C, such as 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40
DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C etc., it is not limited to cited numerical value, other unlisted numbers in the numberical range
It is worth equally applicable.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) porous polymer matrix is prepared, the preparation is drawn using thermally induced phase separation, dry method list, dry method pair is drawn,
In three-layer co-extruded, freezing casting, electrostatic spinning, foaming agent foam or 3D printing any one or at least two combination；
(2) inorganic filler is mixed with the first solvent, obtains the first mixed liquor, porous polymer matrix is soaked in described
In first mixed liquor, soaking temperature is 15~35 DEG C, and soaking time is 10min~30min, separation of solid and liquid obtains that treated base
Material；
Wherein, the mass concentration of inorganic filler is 0.1~10.0g/L in first mixed liquor；
(3) polymer dielectric, lithium salts and the second solvent are mixed, obtains the second mixed liquor；
Wherein, in second mixed liquor, the mass concentration of polymer dielectric is 0.5~10.0g/L；
(4) table of step (1) treated the substrate will be cast in for step (2) second mixed liquor points 3~4 times
Face；
(5) repeat the operation of step (4), and relay upper step in last time casting rear substrate before repeating every time
(2) treated the substrate, duplicate number is 3~5 times, obtains the solid electrolyte after 0~80 DEG C of drying.
The third aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes as described in relation to the first aspect
Solid electrolyte.
Compared with prior art, the invention has the following advantages:
(1) solid electrolyte provided by the invention is using the precisely designed porous polymer matrix skeleton of structure as template
The structural stratification control for realizing organic bath, to realize the accurate control of intensity, help to obtain enhanced electrolyte.This
The conductivity of the solid electrolyte provided is invented up to 7.2 × 10-4S/cm, maximum stress is up to 15.31MPa.
(2) solid electrolyte raw material provided by the invention is simple, wide in variety, alternative strong and cheap and easy to get.
(3) solid electrolyte provided by the invention is controllable with performance, geomery is controllable, elastic and good toughness, cost
Low advantage.
(4) solid electrolyte no leakage provided by the invention, nonflammable, highly-safe.
(5) preparation method provided by the invention is drawn by thermally induced phase separation, dry method list, dry method is double draws, is three-layer co-extruded, cold
Freeze the modes such as casting, electrostatic spinning, foaming agent foam, 3D printing and prepares the porous polymer matrix skeleton as skeleton, it can be right
Skeleton structure, pore size, pore structure, porosity etc. carry out careful design.
(6) preparation method provided by the invention has versatility and simple and easy, environmental-friendly, suitable large-scale industry
Metaplasia produces and promotes business application.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment is prepared as follows solid electrolyte:
(1) there is the membranaceous polyethylene substrate of high porosity of ordered arrangement pore structure by thermally induced phase separation preparation, it is thick
Degree is 5 μm, porosity 60%.
(2) using ethyl alcohol as solvent, inorganic filler magnesia is uniformly mixed, obtains the first mixed liquor (inorganic filler quality
Concentration is 0.2g/L), porous polymer framework is placed in first mixed liquor at 25 DEG C and sufficiently impregnates the 20min time, is made
Inorganic raw material is filled in the pore structure of high hole polyethylene backbone, the substrate that obtains that treated.
(3) using dimethylformamide as solvent, by polymer dielectric polyacrylonitrile and lithium salts LiClO4Uniformly mixing, obtains
To homogeneous solution, as the second mixed liquor (mass concentration of polymer dielectric is 0.5g/L).
(4) step (2) treated substrate surface obtained will be cast in for the second mixed liquor produced above points 3 times；
(5) repeat the operation of step (4), and be poured on the new film surface of rear substrate again in last time before repeating every time
Step (2) treated the substrate is put, duplicate number is 4 times, first in 60 DEG C of vacuum condition dry 5h, places into gloves
Drying at room temperature 10h in case obtains the solid electrolyte.
Solid electrolyte provided in this embodiment includes porous polymer matrix (polyethylene substrate), is located at described porous poly-
Close the inorganic filler (magnesia) in object substrate pores, and the modifier on the porous polymer matrix surface, institute
Modifier is stated by polymer dielectric (polyacrylonitrile) and lithium salts (LiClO4) composition.The modifier is also located at porous polymer
Gap in.Porous polymer matrix is 5 layers of superposition in solid electrolyte, between layers containing described mainly by polymer
The mixture of electrolyte and lithium salts composition, the surface density of porous polymer matrix are 2.2g/m2.The solid electrolyte is film
Shape, with a thickness of 80 μm.In solid electrolyte, porous polymer matrix, inorganic filler, polymer dielectric and lithium salts quality
Than for 0.10:0.35:0.45:0.05.
The performance test results of solid electrolyte provided in this embodiment are shown in Table 1.
Embodiment 2
The present embodiment is prepared as follows solid electrolyte:
(1) the membranaceous polypropylene backbone of high porosity is prepared by dry method list daraf(reciprocal of farad), with a thickness of 12 μm, porosity 60%.
(2) using DMF as solvent, inorganic filler silica is uniformly mixed, obtains the first mixed liquor (inorganic filler quality
Concentration is 0.4g/L), porous polymer framework is placed in first mixed liquor at 15 DEG C and sufficiently impregnates the 10min time, is made
Solid electrolyte raw material is filled up completely in the pore structure of polymer backbone, the substrate that obtains that treated.
(3) using acetonitrile as solvent, by polymer dielectric Kynoar and lithium salts LiCF3SO3Uniformly mixing, preparation are equal
Even solution, as the second mixed liquor (mass concentration of polymer dielectric is 1.0g/L).
(4) the second mixed liquor produced above is cast in step (2) treated substrate surface obtained；
(5) repeat the operation of step (4), and be poured on the new film surface of rear substrate again in last time before repeating every time
Step (2) treated the substrate is put, duplicate number is 5 times, first in 60 DEG C of vacuum condition dry 12h, places into hand
Drying at room temperature 12h in casing obtains the solid electrolyte.
Solid electrolyte provided in this embodiment includes porous polymer matrix (polypropylene base), is located at described porous poly-
The inorganic filler (silica) in object substrate pores, and the modifier on porous polymer matrix surface are closed, it is described
Modifier is by polymer dielectric (Kynoar) and lithium salts (LiCF3SO3) composition.The modifier is also located at porous polymeric
In the gap of object.Porous polymer matrix is 6 layers of superposition in solid electrolyte, between layers containing described mainly by polymerizeing
The mixture of object electrolyte and lithium salts composition, the surface density of porous polymer matrix are 5.2g/L.The solid electrolyte is film
Shape, with a thickness of 120 μm.In solid electrolyte, porous polymer matrix, inorganic filler, polymer dielectric and lithium salts matter
Amount is than being 0.02:0.15:0.55:0.1.
The performance test results of solid electrolyte provided in this embodiment are shown in Table 1.
Embodiment 3
(1) there is the membranaceous polypropylene/polypropylene of high porosity of ordered arrangement pore structure/poly- by the preparation of three-layer co-extruded method
Propylene substrate, with a thickness of 25 μm, porosity 50%.
(2) using acetone as solvent, inorganic filler aluminum oxide is uniformly mixed, obtains the first mixed liquor (inorganic filler
Mass concentration is 0.5g/L), porous polymer framework is placed in when sufficiently impregnating 30min at 35 DEG C in first mixed liquor
Between, it is filled in inorganic raw material in the pore structure of high hole polyethylene backbone, the substrate that obtains that treated.
(3) using acetone as solvent, by polymer dielectric polymethyl methacrylate and lithium salts LiAsF6Uniformly mixing, obtains
To homogeneous solution, as the second mixed liquor (mass concentration of polymer dielectric is 2.5g/L).
(4) step (2) treated substrate surface obtained will be cast in for the second mixed liquor produced above points 4 times；
(5) repeat the operation of step (4), and be poured on the new film surface of rear substrate again in last time before repeating every time
Step (2) treated the substrate is put, duplicate number is 3 times, first in 80 DEG C of vacuum condition dry 5h, places into gloves
Drying at room temperature 10h in case obtains the solid electrolyte.
Solid electrolyte provided in this embodiment includes porous polymer matrix (polypropylene/polypropylene/polypropylene), is located at
Inorganic filler (aluminum oxide) in the porous polymer matrix hole, and it is located at the porous polymer matrix surface
On modifier, the modifier is by polymer dielectric (polymethyl methacrylate) and lithium salts (LiAsF6) composition.It is described
Modifier is also located in poromeric gap.Porous polymer matrix is 4 layers of superposition in solid electrolyte, between layers
Contain the mixture being mainly made of polymer dielectric and lithium salts, the surface density of porous polymer matrix is 11.0g/
m2.The solid electrolyte be it is membranaceous, with a thickness of 130 μm.In solid electrolyte, porous polymer matrix, gathers at inorganic filler
The mass ratio of polymer electrolyte and lithium salts is 0.36:0.15:0.85:0.05.
The performance test results of solid electrolyte provided in this embodiment are shown in Table 1.
Embodiment 4
(1) there is the membranaceous polyethylene substrate of high porosity of ordered arrangement pore structure by thermally induced phase separation preparation, it is thick
Degree is 18 μm, porosity 70%.
(2) using ethyl alcohol as solvent, inorganic filler titanium dioxide is uniformly mixed, obtains the first mixed liquor (inorganic filler matter
Amount concentration is 10.0g/L), porous polymer framework is placed in first mixed liquor at 25 DEG C and sufficiently impregnates the 30min time,
It is filled in inorganic raw material in the pore structure of high hole polyethylene backbone, the substrate that obtains that treated.
(3) using dimethylformamide as solvent, by polymer dielectric polycarbonate and lithium salts LiBF4Uniformly mixing, obtains
To homogeneous solution, as the second mixed liquor (mass concentration of polymer dielectric is 10.0g/L).
(4) the second mixed liquor produced above is cast in step (2) treated substrate surface obtained；
(5) repeat the operation of step (4), and be poured on the new film surface of rear substrate again in last time before repeating every time
Step (2) treated the substrate is put, duplicate number is 3 times, first in 60 DEG C of vacuum condition dry 5h, places into gloves
Drying at room temperature 10h in case obtains the solid electrolyte.
Solid electrolyte provided in this embodiment includes porous polymer matrix (polyethylene substrate), is located at described porous poly-
The inorganic filler (titanium dioxide) in object substrate pores, and the modifier on the porous polymer matrix surface are closed,
The modifier is by polymer dielectric (polycarbonate) and lithium salts (LiBF4) composition.The modifier is also located at porous polymeric
In the gap of object.Porous polymer matrix is 4 layers of superposition in solid electrolyte, between layers containing described mainly by polymerizeing
The mixture of object electrolyte and lithium salts composition, the surface density of porous polymer matrix are 5.65g/m2.The solid electrolyte is
It is membranaceous, with a thickness of 80 μm.In solid electrolyte, porous polymer matrix, inorganic filler, polymer dielectric and lithium salts matter
Amount is than being 0.75:0.85:0.15:0.1.
The performance test results of solid electrolyte provided in this embodiment are shown in Table 1.
Comparative example 1
The solid electrolyte specific method of this comparative example is referring to embodiment 1, and difference is, the soaking process of step (2) is complete
Cheng Hou roasts obtained product, and porous polymer matrix is got rid of by roasting, in the substrate that obtains that treated
Only retain the inorganic filler in porous polymer matrix pore structure and does not contain porous polymer matrix.Only retain nothing with such
The substrate of machine filler carries out the processing such as subsequent casting and repetition, obtains solid electrolyte.
The performance test results for the solid electrolyte that this comparative example provides are shown in Table 1.
Comparative example 2
Referring to embodiment 1, difference is the solid electrolyte specific method of this comparative example, without the operation of step (5),
Operation i.e. without repeating to be poured and repeat to be put into step (2) treated the substrate.
The performance test results for the solid electrolyte that this comparative example provides are shown in Table 1.
Performance test methods
The solid electrolyte that each embodiment and comparative example provides is assembled into button cell in glove box, assembles button cell
Method be full of argon gas glove box in assemble button cell, using lithium piece as cathode, LiFePO4For anode, according to anode-
The solid electrolyte membrane of assembling-lithium piece cathode sequence assembling all solid state lithium ion button cell, wherein positive-active goods and materials are selected
LiFePO4, conductive agent selection conductive black (Super P), binder selection PVDF (HSV900), proportions 90.0:
5.0:5.0 tests the conductivity of button cell with blue electric equipment (model LAND CT2001A) under the conditions of 85 DEG C.
Using the film pull force test method of GB/T1040.3-2006, each embodiment and comparative example is tested under the conditions of 85 DEG C
The maximum stress of the solid electrolyte of offer.
Test result see the table below:
Table 1
Based on the above embodiments it is found that embodiment 1-4 uses scheme provided by the invention to prepare solid electrolyte, Gu
Contain porous polymer matrix in state electrolyte as skeleton, and is added with by being repeated several times to be poured to lay equal stress on into porous polymer matrix
Material realizes the structural stratification control of organic bath, to realize the accurate control of intensity, help to obtain enhanced electrolysis
Matter.The solid electrolyte ionic conductivity and mechanical strength of embodiment 1-4 preparation are all very excellent.
There is no polymeric substrate in solid electrolyte prepared by comparative example 1, is only capable of playing certain support work by inorganic filler
With, therefore its mechanical property is poor, maximum stress is lower, small-sized lamination process is only suitable only for, for the electricity of winding process type
Core, it may appear that large area ceramic bonding loosely with removing the problem of.
Comparative example 2 does not carry out repeating casting and the operation of polymer dielectric is added, this is unfavorable for solid electrolyte
Three-dimensional structure preferably controlled, comparative example 2 provide solid electrolyte in the case of a high temperature polymer present melt or
The unformed state of person, mechanical property significantly reduce.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of solid electrolyte, which is characterized in that the solid electrolyte includes porous polymer matrix, is located at described porous
Inorganic filler in polymeric substrate hole, and the modifier on the porous polymer matrix surface, the modification
Object includes polymer dielectric and alkali metal salt.
2. solid electrolyte according to claim 1, which is characterized in that the porous polymer matrix includes polyvinyl
Appointing in material, polypropylene base, polyethylene/polypropylene/polyethylene substrate, polypropylene/polypropylene/polypropylene base or non-woven fabrics
It anticipates a kind of or at least two combinations；
Preferably, the porosity of the porous polymer matrix is 50~70%；
Preferably, the porous polymer matrix is membranaceous；
Preferably, the porous polymer matrix with a thickness of 5~25 μm；
Preferably, in the solid electrolyte, porous polymer matrix multiple-layer stacked contains the modification between layers
Object；
Preferably, the modifier is also located in poromeric gap；
Preferably, the number of plies of the porous polymer matrix is 4~6 layers；
Preferably, the surface density of the porous polymer matrix is 2.0~13.0g/m2；
Preferably, the solid electrolyte is membranaceous, with a thickness of 80~130 μm.
3. solid electrolyte according to claim 1 or 2, which is characterized in that the inorganic filler includes magnesia, oxidation
In zirconium, calcium carbonate, silica, aluminum oxide, boehmite, titanium dioxide, barium sulfate, calcium sulfate, attapulgite or zeolite
Any one or at least two combination.
4. solid electrolyte according to any one of claim 1-3, which is characterized in that the polymer dielectric includes
Polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, polycarbonate, Kynoar-hexafluoropropene
In dimethyl silicone polymer any one or at least two combination；
Preferably, the alkali metal salt is lithium salts；
Preferably, the lithium salts includes LiClO4、LiPF6、LiAsF6、LiBF4、LiAlCl4、LiSCN、LiTaF6、LiSnF6、
LiGeF6、LiCF3SO3、LiN(SO2CF3)2In LiTFSI any one or at least two combination.
5. solid electrolyte described in any one of -4 according to claim 1, which is characterized in that more in the solid electrolyte
Pore polymer substrate, inorganic filler, polymer dielectric and lithium salts mass ratio be (0.02~0.75): (0.15~0.85):
(0.15~0.85): (0.05~0.15).
6. a kind of preparation method of the solid electrolyte as described in any one of claim 1-5, which is characterized in that the method packet
Include following steps:
(1) substrate that in the gap of inorganic filler filling porous polymer matrix, will obtain that treated；
(2) polymer dielectric and alkali metal salt are assembled in step (1) treated the substrate surface, obtain the solid-state
Electrolyte.
7. the preparation method stated according to office in claim 6, which is characterized in that step (1) is described more by inorganic filler filling
Method in the gap of pore polymer substrate obtains the first mixing the following steps are included: inorganic filler is mixed with the first solvent
Porous polymer matrix is soaked in first mixed liquor by liquid, separation of solid and liquid obtains that treated substrate；
Preferably, first solvent includes any one in dimethylformamide, ethyl alcohol, acetone, tetrahydrofuran or acetonitrile
Or at least two combination；
Preferably, in first mixed liquor, the mass concentration of inorganic filler is 0.1~10.0g/L；
Preferably, the temperature of the immersion is 15~35 DEG C；
Preferably, the time of the immersion is 10~30min；
Preferably, the preparation method of step (1) described porous polymer matrix includes thermally induced phase separation, the drawing of dry method list, dry method
In double drawings, three-layer co-extruded, freezing casting, electrostatic spinning, foaming agent foam or 3D printing any one or at least two group
It closes.
8. preparation method according to claim 6 or 7, which is characterized in that step (2) is described by polymer dielectric and alkali
Metal salt be assembled in the method for step (1) treated the substrate surface the following steps are included:
(2 ') mix polymer dielectric, alkali metal salt and the second solvent, obtain the second mixed liquor；
Step (2 ') second mixed liquor is cast in the surface of step (1) treated the substrate by (2 "), it is dry after
To the solid electrolyte；
Preferably, in step (2 ') second mixed liquor, the mass concentration of polymer dielectric is 0.5~10.0g/L；
Preferably, in step (2 '), second solvent includes in dimethylformamide, ethyl alcohol, acetone, tetrahydrofuran or acetonitrile
Any one or at least two combination；
Preferably, in step (2 "), second mixed liquor is divided 3~4 times and is poured；
Preferably, in step (2 "), further includes: after the casting, repeat step (3) described casting, and repeat every time
It is preceding that upper step (1) treated the substrate is relay in last time casting rear substrate；
Preferably, the duplicate number is 3~5 times；
Preferably, in step (2 "), the method for the drying is that vacuum drying and/or glove box are dry；
Preferably, in step (2 "), the temperature of the drying is 0~80 DEG C.
9. preparation method a method according to any one of claims 6-8, which is characterized in that the described method comprises the following steps:
(1) porous polymer matrix is prepared, the preparation is drawn using thermally induced phase separation, dry method list, the double drawings of dry method, three layers
In co-extrusion, freezing casting, electrostatic spinning, foaming agent foam or 3D printing any one or at least two combination；
(2) inorganic filler is mixed with the first solvent, obtains the first mixed liquor, porous polymer matrix is soaked in described first
In mixed liquor, soaking temperature is 15~35 DEG C, and soaking time is 10~30min, separation of solid and liquid obtains that treated substrate；
Wherein, the mass concentration of inorganic filler is 0.1~10.0g/L in first mixed liquor；
(3) polymer dielectric, lithium salts and the second solvent are mixed, obtains the second mixed liquor；
Wherein, in second mixed liquor, the mass concentration of polymer dielectric is 0.5~10.0g/L；
(4) surface of step (1) treated the substrate will be cast in for step (2) second mixed liquor points 3~4 times；
(5) repeat the operation of step (4), and relay upper step (2) in last time casting rear substrate before repeating every time
Treated the substrate, duplicate number are 3~5 times, obtain the solid electrolyte after 0~80 DEG C of drying.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes as described in any one of claim 1-5
Solid electrolyte.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111463480A (en) * | 2020-03-20 | 2020-07-28 | 东华大学 | Filter membrane based high-performance composite solid electrolyte film and preparation method and application thereof |
| CN113451583A (en) * | 2020-03-27 | 2021-09-28 | 宁德新能源科技有限公司 | Composite current collector, pole piece comprising same, lithium ion battery and electronic device |
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| CN107492681A (en) * | 2017-08-09 | 2017-12-19 | 上海纳晓能源科技有限公司 | Solid electrolyte film and preparation method thereof |
| CN109148945A (en) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | A kind of three-dimensional composite solid electrolyte of structure-controllable and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107492681A (en) * | 2017-08-09 | 2017-12-19 | 上海纳晓能源科技有限公司 | Solid electrolyte film and preparation method thereof |
| CN109148945A (en) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | A kind of three-dimensional composite solid electrolyte of structure-controllable and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111463480A (en) * | 2020-03-20 | 2020-07-28 | 东华大学 | Filter membrane based high-performance composite solid electrolyte film and preparation method and application thereof |
| CN111463480B (en) * | 2020-03-20 | 2022-10-14 | 东华大学 | Filter membrane based high-performance composite solid electrolyte film and preparation method and application thereof |
| CN113451583A (en) * | 2020-03-27 | 2021-09-28 | 宁德新能源科技有限公司 | Composite current collector, pole piece comprising same, lithium ion battery and electronic device |
| CN113451583B (en) * | 2020-03-27 | 2022-08-19 | 宁德新能源科技有限公司 | Composite current collector, pole piece comprising same, lithium ion battery and electronic device |
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