CN109378479A - Solid lithium ion battery electrode slice and preparation method thereof - Google Patents
Solid lithium ion battery electrode slice and preparation method thereof Download PDFInfo
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- CN109378479A CN109378479A CN201811136666.4A CN201811136666A CN109378479A CN 109378479 A CN109378479 A CN 109378479A CN 201811136666 A CN201811136666 A CN 201811136666A CN 109378479 A CN109378479 A CN 109378479A
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- electrode slice
- lithium ion
- active material
- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 77
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000007787 solid Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- -1 vinyl compound Chemical class 0.000 claims abstract description 77
- 239000011149 active material Substances 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 26
- 239000010416 ion conductor Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 21
- 229910052744 lithium Inorganic materials 0.000 description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000006258 conductive agent Substances 0.000 description 13
- 239000011800 void material Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000007784 solid electrolyte Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 7
- 230000037427 ion transport Effects 0.000 description 7
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 150000002466 imines Chemical class 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 3
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002449 FKM Polymers 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 description 2
- 229910010685 Li5La3M2O12 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910012305 LiPON Inorganic materials 0.000 description 2
- 229910013461 LiZr2(PO4)3 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of solid lithium ion battery electrode slice and preparation method thereof and solid lithium ion battery electrode slices.The preparation method of the solid lithium ion battery electrode slice is the following steps are included: configure the electrolyte solution of vinyl compound, lithium salts, initiator, anhydrous solvent, wherein, the vinyl compound is selected from least one of polyenoid based compound, monoene based compound；Battery pole piece is provided, the electrolyte solution is deposited on the battery pole piece and forms liquid film, under conditions of temperature is 50 DEG C -100 DEG C, the liquid film is heated, the electrode slice of electrolyte modification is prepared；Wherein, the battery pole piece includes active material layer, and active material and fast-ionic conductor are at least contained in the active material layer.Solid lithium ion battery electrode slice provided by the invention and preparation method can improve the ion transmission speed of battery pole piece.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of solid lithium ion battery electrode slice and its systems
Preparation Method.
Background technique
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes: when charging, Li+From positive deintercalation,
It is embedded in cathode by electrolyte, cathode is in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery has energy density height, work
The advantages that making voltage height, having extended cycle life, is widely used in the energy storage of mobile electronic device, automobile, electric system etc..
Solid state lithium battery is excellent due to, electrochemical window mouth width good with high-temperature stability, security performance height, energy density height etc.
Point is received significant attention and is studied.Solid state lithium battery lithium ion all more current in terms of cost, energy density and thermal stability
Battery has huge advantage, and the following electric car that will be mainly used in super safe, long continuation of the journey will be the new uncommon of electric car industry
It hopes.The difference of solid state lithium battery and traditional commerce lithium battery is, has used solid electrolyte instead of traditional organic liquid
Electrolyte is as lithium ion transport medium, so overcoming traditional lithium battery electrolytes leakage, the defect of easy firing explosion is improved
Battery safety.Lithium metal can be used as cathode in solid state lithium battery simultaneously, largely improves battery energy
Metric density.However, things all has dual character, on the one hand, interface connects between the solid electrolyte and positive and negative anodes of solid state lithium battery
It is poor to touch, and interface impedance is big；On the other hand, transmission speed of the lithium ion in solid electrolyte will be lower than the biography in liquid electrolyte
Defeated speed, results in that solid state lithium battery internal resistance is very big, and the performance of active material capacity reduces, especially in high rate charge-discharge item
Under part.There is no the infiltration of electrolyte in solid state lithium battery, in positive plate, the transmission of lithium ion can only pass through active material and solid-state
Contact between electrolyte carries out.And the preparation of general solid state battery anode pole piece at present, use positive electrode active materials, solid-state electricity
Solution matter (or PVDF), conductive agent are mixed with slurry, it is necessary to the ratio of solid electrolyte and conductive agent is balanced, ratio is excessively high,
Pole piece ionic conductance improves, but electronic conductance declines；And ratio is too low, electronic conductance is high, and lithium electron conductivity is low.
For anode pole piece ionic conductance problem, polymer solid substantially is mixed into during electrode slice slurry at present
Electrolyte either fast-ionic conductor (such as Li10GeP2S12Or Li7La3Zr2O12).However, the addition of solid electrolyte, certain
The transmission of positive plate inner ion can be improved in degree, but positive plate is after being compacted, it is internal there are still a large amount of hole, hole
It in the presence of lithium ion transport is hindered, causes transmission path elongated, eventually affects the performance of solid lithium ion battery.Therefore, it is
Accelerate the development of solid state cell technology, urgent need to resolve solid state battery positive pole ion transmission problem.
Summary of the invention
The purpose of the present invention is to provide a kind of improvement solid state lithium battery electrode interfaces and room-temperature ion transmission performance to consolidate
State lithium ion battery electrode slice and preparation method thereof, it is intended to it is poor to solve existing solid lithium ion battery positive pole ion transmission performance
The problem of.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of solid lithium ion battery electrode slice, comprising the following steps:
Configure the electrolyte solution of vinyl compound, lithium salts, initiator, anhydrous solvent, wherein the vinyl compound choosing
From at least one of polyenoid based compound, monoene based compound；
Battery pole piece is provided, the electrolyte solution is deposited on the battery pole piece and forms liquid film, to the liquid
Film is heated, and the vinyl compound polymerize under the action of initiator, and the electricity of electrolyte modification is prepared
Pole piece；
Wherein, the battery pole piece includes active material layer, and active material and fast is at least contained in the active material layer
Ion conductor.
Preferably, the vinyl compound is the mixture of polyenoid based compound and monoene based compound.
Preferably, in the vinyl compound, the molar ratio of the polyenoid based compound and the monoene based compound is
1:1~5:2.
Preferably, the polyenoid based compound is selected from least one of diethylenetriamine, double methacrylate class compound.
Preferably, the monoene based compound is selected from acrylic ester compound.
Preferably, it is azodiisobutyronitrile, azobisisoheptonitrile, peroxidating that the initiator, which is initiator selected from initiator,
At least one of benzoyl, dilauryl peroxide, di-tert-butyl peroxide.
Preferably, the quality of the initiator is the 0.3%-3% of the quality of the vinyl compound.
Preferably, the partial size of the fast-ionic conductor is less than the partial size of the active material.
It preferably, is the fast ion in terms of 100% by the active material layer total weight of the electrode slice of electrolyte modification
The total amount percentage composition of conductor is 1%-10%.
Preferably, configure vinyl compound, lithium salts, initiator, anhydrous solvent electrolyte solution method are as follows:
The vinyl compound is dissolved in anhydrous solvent, vinyl compound solution is configured；
The lithium salts is added in the vinyl compound solution, carries out mixed processing, configures electrolyte solution；
Initiator is added in the electrolyte solution, mixed processing obtains the electrolyte solution.
Correspondingly, a kind of solid lithium ion battery electrode slice, the electrode slice includes active material layer, and is filled in
Polymer in the active material layer hole, wherein at least led containing active material and fast ion in the active material layer
Body, the polymer are polymerized for vinyl compound.
Preferably, the vinyl compound is selected from least one of polyenoid based compound, monoene based compound.
Preferably, the weight average molecular weight of the polymer is less than or equal to 2000.
The preparation method of solid lithium ion battery electrode slice provided by the invention deposits alkenes on battery pole piece surface
The electrolyte solution of object, lithium salts, initiator, anhydrous solvent composition is closed, the electrolyte solution infiltrates through battery pole piece internal holes
The internal void of gap, especially active material layer.Further, by heat treatment, the vinyl compound react to be formed it is poly-
Object is closed, so that the mixture that polymer and lithium salts are formed is filled in battery pole piece internal void, forms the electrode of electrolyte modification
Piece.The solid lithium ion battery electrode slice prepared by the method for the invention, can not only improve electrode plates and solid state electrolysis
Interface problem between plasma membrane, and in heat-treatment process, alkenyl compound polymerize in electrode slice internal void, with fastly from
The electrolyte network with three-dimensional diversion is collectively formed in sub- conductor.The electrolyte network of this three-dimensional diversion can not only improve
The ion transmission speed of battery pole piece, and electrode interior electron path will not be destroyed, to will not influence electrode plates electronics
Conductivity finally obtains the solid lithium ion battery electrode slice with preferable electric property.
Solid lithium ion battery electrode slice provided by the invention fills oil polymerization in the active material layer hole
Object can not only improve the interface problem between electrode plates and solid electrolyte membrane, moreover, polymer and fast-ionic conductor are total
There is the electrolyte network of three-dimensional diversion with formation.The electrolyte network of this three-dimensional diversion can not only improve battery pole piece
Ion transmission speed, and electrode interior electron path will not be destroyed, to will not influence electrode plates electronic conductivity, most
The solid lithium ion battery electrode slice with preferable electric property is obtained eventually.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of solid lithium ion battery electrode slice provided in an embodiment of the present invention；
Fig. 2 is the chemical property of the solid lithium ion battery electrode slice of 1-3 of the embodiment of the present invention and the offer of comparative example 1
Test result schematic diagram.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of preparation methods of solid lithium ion battery electrode slice, comprising the following steps:
S01. the electrolyte solution of vinyl compound, lithium salts, initiator, anhydrous solvent is configured, wherein the alkenes chemical combination
Object is selected from least one of polyenoid based compound, monoene based compound；
S02., battery pole piece is provided, the electrolyte solution is deposited on the battery pole piece and forms liquid film, to described
Liquid film is heated, and the vinyl compound polymerize under the action of initiator, and electrolyte modification is prepared
Electrode slice；
Wherein, the battery pole piece includes active material layer, and active material and fast is at least contained in the active material layer
Ion conductor.
The preparation method of solid lithium ion battery electrode slice provided in an embodiment of the present invention deposits on battery pole piece surface
The electrolyte solution that vinyl compound, lithium salts, initiator, anhydrous solvent form, the electrolyte solution infiltrate through battery pole piece
The internal void of internal void, especially active material layer.Further, pass through heat treatment, the vinyl compound reaction
Polymer is formed, so that the mixture that polymer and lithium salts are formed is filled in battery pole piece internal void, forms electrolyte modification
Electrode slice.The solid lithium ion battery electrode slice of method preparation through the embodiment of the present invention, can not only improve electrode pole
Interface problem between piece and solid electrolyte membrane, and in heat-treatment process, alkenyl compound is in electrode slice internal void
The electrolyte network with three-dimensional diversion is collectively formed with fast-ionic conductor in middle polymerization.The electrolyte of this three-dimensional diversion
Network not only accelerates the transmission of electrode slice inner ion, can improve the ion transmission speed of battery pole piece, and will not destroy
Electrode interior electron path finally obtains consolidating with preferable electric property to will not influence electrode plates electronic conductivity
State lithium ion battery electrode slice.
Specifically, the electrolyte solution of vinyl compound, lithium salts, initiator, anhydrous solvent is configured in above-mentioned steps S01,
For being penetrated into following step in the internal void of battery pole piece, especially internal holes of battery pole piece active material layer
In gap, for improving the interface problem between electrode plates and solid electrolyte membrane, improve the ion transmission speed of battery pole piece
And electronic conductivity.
The vinyl compound not only has reactivity, can polymerize to form high-molecular compound；Importantly, alkene
The polymer ionic conductivity with higher that class compound is formed, so that the introducing due to other high molecular materials be avoided to cause
The problem of lithium ion conductivity reduces.
Specifically, the vinyl compound is selected from least one of polyenoid based compound, monoene based compound.It is described more
Alkenyl compound, monoene based compound belong to small molecule compound, are dissolved in organic solvent, may penetrate into positive plate after forming solution
Pore interior heats under the conditions of existing for the initiator, can polymerize, polymerize formation polymer dielectric have it is lower
Molecular weight, such oligomer ionic conductivity with higher can largely improve the transmission of pole piece inner ion.But in this way
Oligomer, molecule segment is short, and film forming is poor, is not suitable for individually being used as polymer dielectric film.
In some embodiments, the vinyl compound selects monoene based compound.Selection monoene based compound is gathered
When closing reaction, since polymerization reaction site is less, polymerization reaction is easy to interrupt, and obtained polymer molecular weight is relatively small, shape
At polymer can effectively transmit lithium ion.In some embodiments, the monoene based compound is selected from esters of acrylic acid
Close object.Acrylic ester compound molecular weight is small, can preferably control the molecular size of its polymer, esters of acrylic acid
The molecular weight polymers that object is formed are closed, lithium ion can be effectively transmitted.
In some embodiments, the vinyl compound is the mixture of polyenoid based compound and monoene based compound, special
Not You Xuanwei diene based compound and monoene based compound mixture.When using diene based compound and monoene based compound
When mixture, in the internal void of battery pole piece, the polymer of formation can form network structure to a certain degree, be conducive to mention
The ion of high electrode piece transmits.It is worth noting that, preferably not using its other than polyenoid based compound in the embodiment of the present invention
The material base of his polyenoid based compound as the internal void of filling battery pole piece, mainly polyenoid based compound are anti-in polymerization
At once, since reaction site is excessive, polymerization reaction is difficult to terminate, and finally obtained polymer is since molecular weight is excessively high, knife lithium
Ion laser propagation effect reduces.In some embodiments, the polyenoid based compound is selected from diethylenetriamine, double methacrylate class
Close at least one of object.Preferred above-mentioned diethylenetriamine, double methacrylate class compound, molecular size is suitable, with monoene
Based compound is blended, and is conducive to the degree for controlling polymerization reaction, the relatively low polymer of molecular weight is obtained, to be filled in electricity
In the internal void of pond pole piece, particularly the internal void of battery pole piece active material layer.Importantly, diethylenetriamine,
The polymer that double methacrylate class compound is formed, can effectively transmit lithium ion.
It is further preferred that the polyenoid based compound rubs with the monoene based compound in the vinyl compound
You are than being 1:1~5:2, and particularly preferably the molar ratio of diene based compound and monoene based compound is 1:1~5:2.The two contains
In the range, the lithium ion transport efficiency and electrochemical stability of obtained battery pole piece are more preferably for amount.
In some embodiments, the lithium salts is selected from bis trifluoromethyl sulphur imine lithium, trifluoromethyl sulfonic acid lithium, perchloric acid
At least one of lithium, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium.
Further, in the electrolyte solution solution, the quality of the lithium salts is the 20%-100% of the vinyl compound quality.
If the lithium salt content is too low, battery conductance rate is reduced；If the lithium salt content is excessively high, lithium salts is due to reuniting, together
Sample can reduce electrolytic conductivity.
In some embodiments, it be initiator is azodiisobutyronitrile, azo two different heptan that the initiator, which is selected from initiator,
At least one of nitrile, benzoyl peroxide, dilauryl peroxide, di-tert-butyl peroxide.Above-mentioned initiator, can
Effectively cause the polymerization reaction between polyenoid based compound, meanwhile, other side reactions between raw material will not be introduced.
Preferably, the quality of the initiator is the 0.3%-3% of the quality of the vinyl compound.If the initiator
Content it is too low, then be difficult to cause the polymerization reaction between vinyl compound, or even cannot cause poly- between vinyl compound
Close reaction；If the too high levels of the initiator, initiator is remained in the electrolyte, in lithium ion battery charge and discharge process
Side reaction occurs, influences performance of lithium ion battery, the capacity that may cause lithium ion battery reduces.
Specifically, the anhydrous solvent as solvent, can not only preferably dissolve vinyl compound, lithium salts, initiator, and
Even and if also not reacting in a heated condition with any one in above-mentioned raw materials.Preferably, the anhydrous solvent is selected from
At least one of acetonitrile, tetrahydrofuran, dimethyl sulfoxide, chlorobenzene, succinonitrile, toluene, propene carbonate, ionic liquid.It is excellent
The anhydrous solvent of choosing has preferable dissolubility, meanwhile, boiling point is lower, is conducive to remove by heating.
Preferably, configure vinyl compound, lithium salts, initiator, anhydrous solvent electrolyte solution method are as follows:
S011. the vinyl compound is dissolved in anhydrous solvent, configures vinyl compound solution；
S012. the lithium salts is added in the vinyl compound solution, carries out mixed processing, configures electrolyte solution；
S013. initiator is added in the electrolyte solution, mixed processing obtains the electrolyte solution.
In this way, vinyl compound is first dissolved in anhydrous solvent to be dissolved in anhydrous solvent, configures alkenes chemical combination
After object is dissolved in anhydrous solvent solution, lithium salts is added, through mixed processing, so that the two uniformly mixes, it is molten when being deposited on pole piece
Liquid can penetrate into the internal void of battery pole piece, be uniformly filled in electrode slice internal voids after polymerization, so that electrode slice
Inside forms the ion transmission network of Complete three-dimensional, improves ion transmission speed.
The embodiment of the present invention directly the initiator and vinyl compound and lithium salts is not added simultaneously, but in alkenes
Initiator is added in the mixed solution for closing object and lithium salts, so that initiator be avoided to add overlong time, electrolyte solution is not being deposited
It is such as coated in pole piece to go forward that certain polymerization occurs, forms biggish polymer, influence infiltration of the electrolyte inside pole piece.
In above-mentioned steps S02, battery pole piece is provided, is at least led containing active material and fast ion in the active material layer
Body.
In some embodiments, the active material is in LiFePO4, cobalt acid lithium, LiMn2O4 or nickle cobalt lithium manganate
It is at least one.Further, mass percentage of the active material in the electrode slice active material layer is 70-
95%.
The fast-ionic conductor ion transmission efficiency with higher is conducive to improve electrode spy as solid electrolyte
It is not the lithium ion transport efficiency of positive plate.Specifically, the partial size of the fast-ionic conductor is less than the partial size of the active material,
So that fast-ionic conductor can be good at being distributed in around active material.
It preferably, is the fast ion in terms of 100% by the active material layer total weight of the electrode slice of electrolyte modification
The total amount percentage composition of conductor is 1%-10%.The total amount percentage composition of fast-ionic conductor within this range, can not only provide
Preferable lithium ion transport efficiency moreover, can guarantee the content of active material, and then assigns the preferable energy of solid lithium ion battery
Metric density.If the total amount percentage composition of the fast-ionic conductor is higher than 10%, the relative amount of active material declines, battery energy
Metric density decline.
In some embodiments, the fast-ionic conductor is Li3aLa(2/3)-aTiO3(0.04<a<0.14)、Li 3+ aXaY1-aO4(X=Si, Sc, Ge, Ti；Y=P, As, V, Cr；0<a<1),LiZr2(PO4)3、Li7La3Zr2O12、Li1+ aAlaTibGe2-a-b(PO4)(0<a<1；0≤b<2),Li3OCl、Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、
Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX (X=Cl, Br, I), Li9-naMaN2Cl (M=Na,
K,Rb,Cs,Mg,Al；0<a<0.2；0<n<10),3Li3N-MI (M=Li, Na, K), LiPON, Li2S-MSa(M=Al, Si, P；1
< a < 3) one or more.
In some embodiments, conductive agent, active material and fast-ionic conductor are at least contained in the active material layer.Its
In, the conductive agent can be in conductive black, acetylene black, super P, carbon nanotube, carbon nano-fiber
It is one or more of.Further, described in terms of by the active material layer total weight of the electrode slice of electrolyte modification for 100%
The total amount percentage composition of conductive agent is 1-15%.
In some embodiments, binder, conductive agent, active material and fast ion are at least contained in the active material layer
Conductor.Wherein, the binder can be in Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, Viton
One or more.It further, is institute in terms of 100% by the active material layer total weight of the electrode slice of electrolyte modification
The total amount percentage composition for stating conductive agent is 1-15%.
In some embodiments, the battery pole piece can be prepared by following methods: by active material, conductive agent
Ground and mixed is uniform in proportion with fast-ionic conductor, obtains mixing material；Prepared bonding is added into above-mentioned mixing material
Agent solution is mixed to get evenly dispersed, viscosity slurry appropriate；Above-mentioned paste deposition is prepared into pole piece on matrix, is dried, roller
Pressure, obtains required electrode slice.
In some embodiments, the battery pole piece further includes collector, and the active material layer is arranged in the afflux
On body.The electrolyte solution is deposited on the surface that the active material layer deviates from the collector.
In the embodiment of the present invention, the electrolyte solution is deposited on the battery pole piece and forms liquid film, electrolyte is molten
Liquid will infiltrate through inside electrode slice, be filled in electrode material gap, and a thin layer of electrolyte solution is formed in electrode surface
State layer.The electrolyte solution is deposited on the battery pole piece and forms liquid film, and conventional solution processing method can be used and realize,
Including but not limited to scratch.
The liquid film is heated, the vinyl compound polymerize under the action of initiator, is formed
Oligomer is filled in the pore structure of battery pole piece.Preferably, the temperature of the heat treatment is 50-100 DEG C, the temperature model
It encloses, not only can guarantee effective generation of vinyl compound polymerization reaction, moreover, other miscellaneous side reactions will not be introduced.Meanwhile it will not
The substance and its structure of the active material layer of formation are damaged or other influences.
The preparation method of solid lithium ion battery electrode slice provided in an embodiment of the present invention can be prepared following solid
The electrode slice of state lithium ion battery.
Correspondingly, the embodiment of the invention provides a kind of solid lithium ion battery electricity consumptions being prepared by the above method
Pole piece.
And in conjunction with Fig. 1, the embodiment of the invention also provides a kind of solid lithium ion battery electrode slice, the electrodes
Piece includes active material layer 1, and the polymer 11 being filled in 1 hole of active material layer, wherein the active material
At least contain active material 12 and fast-ionic conductor 13 in layer, the polymer is polymerized for vinyl compound.
Solid lithium ion battery electrode slice provided in an embodiment of the present invention fills oil in the active material layer hole
Polymer can not only improve the interface problem between electrode plates and solid electrolyte membrane, moreover, polymer is led with fast ion
The electrolyte network with three-dimensional diversion is collectively formed in body.The electrolyte network of this three-dimensional diversion can not only improve battery
The ion transmission speed of pole piece, and electrode interior electron path will not be destroyed, to will not influence electrode plates electronic conductance
Rate finally obtains the solid lithium ion battery electrode slice with preferable electric property.
The solid lithium ion battery can be all solid state serondary lithium battery, or quasi- solid-state serondary lithium battery.
The electrode slice includes active material layer, and active material and fast-ionic conductor are at least contained in the active material layer.
In some embodiments, the active material 12 is in LiFePO4, cobalt acid lithium, LiMn2O4 or nickle cobalt lithium manganate
At least one.Further, mass percentage of the active material 12 in the electrode slice active material layer 1 is
70-95%.
The fast-ionic conductor 13 ion transmission efficiency with higher is conducive to improve electrode as solid electrolyte
The especially lithium ion transport efficiency of positive plate.Specifically, the partial size of the fast-ionic conductor 13 is less than the active material 12
Partial size.It preferably, is the fast ion in terms of 100% by 1 total weight of active material layer of the electrode slice of electrolyte modification
The total amount percentage composition of conductor 13 is 1%-10%.
In some embodiments, the fast-ionic conductor 13 is Li3aLa(2/3)-aTiO3(0.04<a<0.14)、Li 3+ aXaY1-aO4(X=Si, Sc, Ge, Ti；Y=P, As, V, Cr；0<a<1),LiZr2(PO4)3、Li7La3Zr2O12、Li1+ aAlaTibGe2-a-b(PO4)(0<a<1；0≤b<2),Li3OCl、Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、
Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX (X=Cl, Br, I), Li9-naMaN2Cl (M=Na,
K,Rb,Cs,Mg,Al；0<a<0.2；0<n<10),3Li3N-MI (M=Li, Na, K), LiPON, Li2S-MSa(M=Al, Si, P；1
< a < 3) one or more.
In some embodiments, it is at least led containing conductive agent 14, active material 11 and fast ion in the active material layer 1
Body 12.Wherein, the conductive agent 14 can be selected from but not limited to conductive black, acetylene black, super P, carbon nanotube, carbon nanometer
One or more of fiber.Further, it is with 1 total weight of active material layer of the electrode slice of electrolyte modification
100% meter, the total amount percentage composition of the conductive agent 14 are 1-15%.
In some embodiments, in the active material layer 1 at least containing binder (not marked in figure), conductive agent 14,
Active material 12 and fast-ionic conductor 13.Wherein, the binder can be selected from but not limited to Kynoar, polytetrafluoroethyl-ne
One or more of alkene, butadiene-styrene rubber, Viton.Further, with the active material of the electrode slice of electrolyte modification
Bed of material total weight is 100% meter, and the total amount percentage composition of the conductive agent is 1-15%.
In some embodiments, the battery pole piece further includes collector 2, and the active material layer 1 is arranged in the collection
On fluid 2.
Contain gap structure in the active material layer 1 of the electrode slice, the presence of hole hinders lithium ion transport, causes
Transmission path is elongated, eventually affects the performance of solid lithium ion battery.In consideration of it, in the embodiment of the present invention, using polymer
11 are filled in 1 hole of active material layer, and the interface that can not only improve between electrode plates and solid electrolyte membrane is asked
Topic, moreover, the electrolyte network with three-dimensional diversion is collectively formed in polymer and fast-ionic conductor.This three-dimensional diversion
Electrolyte network can not only improve the ion transmission speed of battery pole piece, and will not destroy electrode interior electron path, thus
It will not influence electrode plates electronic conductivity, finally obtain the solid lithium ion battery electrode slice with preferable electric property.
The polymer 11 is polymerized for vinyl compound, and polymer formed by vinyl compound itself is to lithium ion
With certain conduction, so that the introducing due to other high molecular materials be avoided to lead to asking for lithium ion conductivity reduction
Topic.
In some embodiments, the vinyl compound in polyenoid based compound, monoene based compound at least one
Kind.Preferably, the polyenoid based compound selects diene based compound.In some embodiments, the polyenoid based compound choosing
From at least one of diethylenetriamine, double methacrylate class compound.In some embodiments, the monoene based compound choosing
From acrylic ester compound.
In some embodiments, the vinyl compound selects polyenoid based compound, especially diene based compound.One
In a little embodiments, the vinyl compound selects monoene based compound.In some embodiments, the vinyl compound is polyenoid
The mixture of based compound and monoene based compound, the particularly preferably mixture of diene based compound and monoene based compound.
It is further preferred that the molar ratio of the polyenoid based compound and the monoene based compound is 1:1 in the vinyl compound
The molar ratio of~5:2, particularly preferably diene based compound and monoene based compound is 1:1~5:2.
In some embodiments, the lithium salts is selected from bis trifluoromethyl sulphur imine lithium, trifluoromethyl sulfonic acid lithium, perchloric acid
At least one of lithium, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium.
Further, in the electrolyte solution solution, the quality of the lithium salts is the 20%-100% of the vinyl compound quality.
On the basis of the above embodiments, it is preferred that the weight average molecular weight of the polymer is less than or equal to 2000, to protect
Demonstrate,proving it can effectively fill in gap structure.
The embodiment of the invention also provides a kind of solid lithium ion battery, including electrode slice, the electrode slice is above-mentioned
Solid lithium ion battery electrode slice.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of solid lithium ion battery electrode slice, comprising the following steps:
Positive plate preparation: by 8g LiFePO4、0.5g super P、1g Li7La3Zr2O12Ball milling 2h is uniformly mixed, and is added
The PVDF binder (PVDF is the glue being dissolved in NMP) of 0.5g stirs 2-5h, is sufficiently mixed uniformly, it is appropriate to obtain viscosity
Slurry.Slurry is scratched in aluminium foil surface, 60~100 DEG C of dry 2-10h.After roll-in, punching, 80 DEG C of vacuum drying, pole piece claims
Weight.
Electrode slice is modified solution and is prepared: in molar ratio by polyethyleneglycol diacrylate and polyethylene glycol methacrylate-styrene polymer
The ratio of 1:1~5:2 is dissolved in a small amount of acetonitrile, and bis trifluoromethyl sulphur imine lithium is added, stirs.Then propylene is added
The azodiisobutyronitrile of acid esters mass fraction 0.5% stirs 2h, is uniformly mixed.
It modifies positive plate preparation: the solution of above-mentioned preparation being coated on the positive plate of above-mentioned preparation, in dry environments,
60 DEG C of polymerization 12h are forming one layer 1~10 μm of electrolyte layer, are obtaining the positive plate of electrolyte modification.
Embodiment 2
A kind of preparation method of solid lithium ion battery electrode slice, comprising the following steps:
Positive plate preparation: by 8g LiFePO4、0.5g super P、1g Li1.3Al0.3Ti1.7(PO4)3Ball milling 2h mixing is equal
It is even, PVDF binder (PVDF is the glue being dissolved in NMP) the stirring 2-5h of 0.5g is added, is sufficiently mixed uniformly, is sticked
Spend slurry appropriate.Slurry is scratched in aluminium foil surface, 60~100 DEG C of dry 2-10h.After roll-in, punching, 80 DEG C of vacuum are dry
It is dry, pole piece weighing.
Electrode slice is modified solution and is prepared: in molar ratio by polyethyleneglycol diacrylate and polyethylene glycol methacrylate-styrene polymer
The ratio of 1:1~5:2 is dissolved in a small amount of acetonitrile, and bis trifluoromethyl sulphur imine lithium is added, stirs.Then propylene is added
The azodiisobutyronitrile of acid esters mass fraction 0.5% stirs 2h, is uniformly mixed.
It modifies positive plate preparation: the solution of above-mentioned preparation being coated on the positive plate of above-mentioned preparation, in dry environments,
60 DEG C of polymerization 12h are forming one layer 1~10 μm of electrolyte layer, are obtaining the positive plate of electrolyte modification.
Embodiment 3
A kind of preparation method of solid lithium ion battery electrode slice, comprising the following steps:
Positive plate preparation: by 8g LiFePO4、0.5g super P、1g Li7La3Zr2O12Ball milling 2h is uniformly mixed, and is added
The PVDF binder (PVDF is the glue being dissolved in NMP) of 0.5g stirs 2-5h, is sufficiently mixed uniformly, it is appropriate to obtain viscosity
Slurry.Slurry is scratched in aluminium foil surface, 60~100 DEG C of dry 2-10h.After roll-in, punching, 80 DEG C of vacuum drying, pole piece claims
Weight.
Electrode slice modification solution is prepared: polyethylene glycol methacrylate-styrene polymer being dissolved in a small amount of acetonitrile, double fluoroforms are added
Base sulphur imine lithium, stirs.Then the azodiisobutyronitrile of acrylate mass fraction 0.5% is added, stirs 2h, mixes
It closes uniform.
It modifies positive plate preparation: the solution of above-mentioned preparation being coated on the positive plate of above-mentioned preparation, in dry environments,
60 DEG C of polymerization 12h are forming one layer 1~10 μm of electrolyte layer, are obtaining the positive plate of electrolyte modification.
Comparative example 1
A kind of preparation method of solid lithium ion battery electrode slice, comprising the following steps:
Positive plate preparation: by 8g LiFePO4、0.5g super P、1g Li7La3Zr2O12Ball milling 2h is uniformly mixed, and is added
The PVDF binder (PVDF is the glue being dissolved in NMP) of 0.5g stirs 2-5h, is sufficiently mixed uniformly, it is appropriate to obtain viscosity
Slurry.Slurry is scratched in aluminium foil surface, 60~100 DEG C of dry 2-10h.After roll-in, punching, 80 DEG C of vacuum drying, pole piece claims
Weight.
The electrochemical property test result signal for the solid lithium ion battery electrode slice that embodiment 1-3, comparative example 1 provide
Figure is as shown in Fig. 2, from Figure 2 it can be seen that the conductivity of solid lithium ion battery electrode slice provided in an embodiment of the present invention improves, appearance
Amount increases.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of solid lithium ion battery electrode slice, which comprises the following steps:
Configure the electrolyte solution of vinyl compound, lithium salts, initiator, anhydrous solvent, wherein the vinyl compound is selected from more
At least one of alkenyl compound, monoene based compound；
Battery pole piece is provided, the electrolyte solution is deposited on the battery pole piece and forms liquid film, to the liquid film into
Row heat treatment, the vinyl compound polymerize under the action of initiator, and the electrode slice of electrolyte modification is prepared；
Wherein, the battery pole piece includes active material layer, and active material and fast ion are at least contained in the active material layer
Conductor.
2. the preparation method of solid lithium ion battery electrode slice as described in claim 1, which is characterized in that the alkenes
Close the mixture that object is polyenoid based compound and monoene based compound.
3. the preparation method of solid lithium ion battery electrode slice as claimed in claim 2, which is characterized in that the alkenes
It closes in object, the molar ratio of the polyenoid based compound and the monoene based compound is 1:1~5:2.
4. the preparation method of solid lithium ion battery electrode slice as claimed in claim 2 or claim 3, which is characterized in that described more
Alkenyl compound is selected from least one of diethylenetriamine, double methacrylate class compound；And/or
The monoene based compound is selected from acrylic ester compound.
5. the preparation method of solid lithium ion battery electrode slice as described in any one of claims 1-3, which is characterized in that institute
Stating initiator and being selected from initiator be initiator is azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dilauryl mistake
At least one of oxide, di-tert-butyl peroxide；And/or
The quality of the initiator is the 0.3%-3% of the quality of the vinyl compound.
6. the preparation method of solid lithium ion battery electrode slice as described in any one of claims 1-3, which is characterized in that institute
The partial size for stating fast-ionic conductor is less than the partial size of the active material.
7. the preparation method of solid lithium ion battery electrode slice as described in any one of claims 1-3, which is characterized in that with
The active material layer total weight of the electrode slice of the electrolyte modification is 100% meter, and the total amount percentage of the fast-ionic conductor contains
Amount is 1%-10%.
8. the preparation method of solid lithium ion battery electrode slice as described in any one of claims 1-3, which is characterized in that match
Set vinyl compound, lithium salts, initiator, anhydrous solvent electrolyte solution method are as follows:
The vinyl compound is dissolved in anhydrous solvent, vinyl compound solution is configured；
The lithium salts is added in the vinyl compound solution, carries out mixed processing, configures electrolyte solution；
Initiator is added in the electrolyte solution, mixed processing obtains the electrolyte solution.
9. a kind of solid lithium ion battery electrode slice, which is characterized in that the electrode slice includes active material layer, and filling
Polymer in the active material layer hole, wherein at least contain active material and fast ion in the active material layer
Conductor, the polymer are polymerized for vinyl compound.
10. solid lithium ion battery electrode slice as claimed in claim 9, which is characterized in that the vinyl compound is selected from
At least one of polyenoid based compound, monoene based compound；And/or
The weight average molecular weight of the polymer is less than or equal to 2000.
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| CN113258132A (en) * | 2021-05-11 | 2021-08-13 | 合肥工业大学 | Solid electrolyte, preparation method thereof and solid battery |
| CN114464766A (en) * | 2020-11-09 | 2022-05-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel negative electrode structure, preparation method thereof and battery |
| CN114464765A (en) * | 2020-11-09 | 2022-05-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel positive electrode structure, preparation method thereof and battery |
| CN115353154A (en) * | 2022-08-08 | 2022-11-18 | 南通金通储能动力新材料有限公司 | Solid-state lithium ion battery anode material precursor and preparation method thereof |
| CN116093253A (en) * | 2023-04-12 | 2023-05-09 | 四川新能源汽车创新中心有限公司 | Battery pole piece, preparation method thereof and semi-solid lithium ion battery |
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2018
- 2018-09-28 CN CN201811136666.4A patent/CN109378479A/en active Pending
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| CN114464765A (en) * | 2020-11-09 | 2022-05-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel positive electrode structure, preparation method thereof and battery |
| CN114464765B (en) * | 2020-11-09 | 2024-05-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel positive electrode structure, preparation method thereof and battery |
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| CN115353154A (en) * | 2022-08-08 | 2022-11-18 | 南通金通储能动力新材料有限公司 | Solid-state lithium ion battery anode material precursor and preparation method thereof |
| CN115353154B (en) * | 2022-08-08 | 2023-07-14 | 南通金通储能动力新材料有限公司 | Solid-state lithium ion battery anode material precursor and preparation method thereof |
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| CN116111038A (en) * | 2023-04-12 | 2023-05-12 | 四川新能源汽车创新中心有限公司 | Electrode plate, preparation method thereof and lithium battery |
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