CN109378521A - Inorganic-organic composite solid electrolyte, preparation method thereof and assembled all-solid-state lithium battery - Google Patents
Inorganic-organic composite solid electrolyte, preparation method thereof and assembled all-solid-state lithium battery Download PDFInfo
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- CN109378521A CN109378521A CN201811222182.1A CN201811222182A CN109378521A CN 109378521 A CN109378521 A CN 109378521A CN 201811222182 A CN201811222182 A CN 201811222182A CN 109378521 A CN109378521 A CN 109378521A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 24
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 14
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- -1 hexafluoroarsenate lithium Chemical compound 0.000 claims description 11
- 150000002466 imines Chemical class 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000010954 inorganic particle Substances 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 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 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 3
- 229910013098 LiBF2 Inorganic materials 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 2
- 239000002609 medium Substances 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002612 dispersion medium Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 22
- 229920005596 polymer binder Polymers 0.000 abstract 2
- 239000002491 polymer binding agent Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- 229920002050 silicone resin Polymers 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 description 19
- 238000002604 ultrasonography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 210000000170 cell membrane Anatomy 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910013410 LiNixCoyAlzO2 Inorganic materials 0.000 description 1
- 229910013706 LiNixMnyCozO2 (NMC) Inorganic materials 0.000 description 1
- OUGOOSHGPCBMLD-UHFFFAOYSA-N [B].FOC(C(=O)OF)=O Chemical compound [B].FOC(C(=O)OF)=O OUGOOSHGPCBMLD-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052635 ferrosilite Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- 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)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses an inorganic-organic composite solid electrolyte, a preparation method thereof and an assembled all-solid-state lithium battery, wherein the composition of the inorganic-organic composite solid electrolyte comprises one or more of polymer binder styrene-butadiene rubber, nitrile rubber, polyacrylonitrile, silicone resin or derivatives thereof, lithium salt and inorganic nano-particles, wherein the mass percentage content of the polymer binder in the electrolyte is 5-60%; the mass percentage content of the lithium salt in the electrolyte is 10-80%; the mass percentage content of the inorganic nano particles in the electrolyte is 10-40%. The ionic conductivity at room temperature is higher, the electrochemical window is wider and the mechanical property is better; the preparation method of the composite solid electrolyte is easy to prepare a large-area solid electrolyte film; the composite solid electrolyte has higher mechanical property and excellent electrochemical stability, and the assembled battery has stable cycle performance and higher capacity exertion.
Description
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of inorganic-organic hybrid solid electrolyte and its system
Preparation Method and the solid lithium battery of assembling.
Background technique
Lithium ion battery as a kind of high-efficiency energy-storage device, have light, small in size, energy density is high, output power is high,
The advantages that service life length, output voltage height, memory-less effect, non-environmental-pollution, it is widely used in portable number 3C equipment, new energy
The fields such as automobile, unmanned plane, extensive energy storage.
Commercial li-ion battery is generally using flammable liquid organic solvent as electrolyte at present, therefore volatile and inflammable
It burns, lithium ion battery is caused to there are the security risks such as kindling, explosion.Although having various safeguard measures, nothing in practical application
Method fundamentally changes the inflammable chemical nature of electrolyte.Solid lithium battery is taken with non-volatile, nonflammable solid electrolyte
Generation, therefore can fundamentally solve the safety problem of lithium battery.In addition, can further mitigate battery using solid electrolyte
Quality promotes battery energy density.
The all solid state electrolyte that the difficult point of solid lithium battery technology essentially consists in high ionic conductivity and is easy to form a film
The method that solid electrolyte slurry is directly coated at electrode surface, is commonly often difficult in electrode layer and solid-state by the preparation of layer
Form good physical contact between electrolyte layer, and more mature vacuum PVD method, at high cost, low efficiency, institute
The battery capacity of preparation is general also smaller, is not able to satisfy the demand of the large-scale production of all-solid-state battery.Therefore, one kind is developed
Have both high-performance, the all-solid-state battery electrolyte layer of easily many good characteristics such as preparation is just particularly important and urgent.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of inorganic-organic hybrid solid electrolyte and its preparation sides
Method and the solid lithium battery of assembling improve the physical contact between pole piece and electrolyte layer, realize that interface lithium ion is quick
Transmission.Electrolyte layer preparation provided by the invention is simple, has excellent performance, and is suitble to scale amplification production.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: a kind of inorganic-organic hybrid solid state electrolysis
Matter includes the following components'mass percentage:
Polymeric binder 5%-60%
Lithium salts 10%-80% with ionic conductivity
Inorganic nanoparticles 10%-40%
The polymeric binder, including the derivative polyacrylonitrile containing acrylonitrile, styrene or Gui Yang functional group, fourth
One or more of nitrile rubber, butadiene rubber, butadiene-styrene rubber, hydrogenated nitrile-butadiene rubber, silica resin or derivatives thereof.
The lithium salts with ionic conductivity is lithium perchlorate LiClO4, hexafluoroarsenate lithium LiAsF6, LiBF4
LiBF4, lithium hexafluoro phosphate LiPF6, trifluoromethyl sulfonic acid lithium LiCF3SO3, bis- (trifluoromethane sulfonic acid) imine lithium LiTFSi, three
(trifluoromethane sulfonic acid) lithium methide LiC (CF3SO2)3, di-oxalate lithium borate LiBOB, difluoro (oxalic acid) lithium borate LiBF2(C2O4),
Bis- (fluorine sulphonyl) imine lithium LiFSi, one of difluorine oxalic acid boracic acid lithium LiODFB or several.
The inorganic nanoparticles are active fast-ionic conductor or inert inorganic particle.
The activity fast-ionic conductor is Li7La3Zr2O12, LixLa2/3-xTi03, Li1+xAlxTi2-x(PO4)3, LiAlO2,
Li7-xLa3Zr2-xMxO12, Li10GeP2S12, yLi2S·(100-y)P2S5One or more of, wherein M=Ta, Nb, 0.25 < x
<2,30≤y≤70。
The inert inorganic particle is SiO2、ZrO2、Al2O3、TiO2、BaTiO3One or more of.
The preparation method of above-mentioned inorganic-organic hybrid solid electrolyte, comprising the following steps:
Polymeric binder is added in decentralized medium according to the mass ratio of 1-4:30, is stirred at room temperature by step 1
It mixes, ultrasound is made into uniform polymer bonding agent solution；
Lithium salts and inorganic nanoparticles are added in the polymer bonding agent solution of step 1 preparation step 2, stirring
Uniform polymeric binder-lithium salts-inorganic nanoparticles slurry is obtained afterwards；
Polymeric binder-lithium salts-inorganic nanoparticles slurry obtained in step 2 is coated on polytetrafluoro by step 3
Solid-state electricity in vinyl plate, in an inert atmosphere by being dried in vacuo 12h at 50 DEG C, after sufficiently dry removal decentralized medium
Solution plasma membrane is removed from ptfe substrate, obtains solid electrolyte membrane.
The decentralized medium is one or more of carbonic ester, aromatic hydrocarbon, tertiary amine, ethers.
Coating method is using blade coating, spraying, spin coating or electrostatic applications in the step 3.
A kind of solid lithium battery of inorganic-organic hybrid solid electrolyte assembling, including anode, cathode and between two
Solid electrolyte between person, anode include plus plate current-collecting body, positive electrode active materials, conductive agent, binder；Cathode includes lithium gold
One of category, lithium metal alloy.
The positive electrode active materials include the lithium metal oxide of stratiform, the material of spinel structure, polyanionic structure
One or more of material.
The beneficial effects of the present invention are: conductivity at room temperature with higher at room temperature, wider electrochemical window and
More excellent mechanical performance；Composite solid electrolyte mechanical performance with higher and excellent electrochemical stability, assembling
Battery capacity with higher plays and stablizes cycle performance.
Detailed description of the invention
Fig. 1 is the AC impedance spectroscopy of the composite solid electrolyte film in the embodiment of the present invention one；
Fig. 2 be the present invention using the button electricity of the composite solid electrolyte film assembling in embodiment one under 0.1C multiplying power for the first time
Charging and discharging curve figure (cobalt acid lithium LiCoO2/ lithium metal)；
Fig. 3 is the button electricity of the invention using the composite solid electrolyte film assembling in embodiment one under different multiplying
Cycle performance figure (the cobalt acid lithium LiCoO of (0.1C-1C)2/ lithium metal)；
Fig. 4 be the present invention using the button electricity of the composite solid electrolyte film assembling in embodiment one under 0.1C multiplying power for the first time
Charging and discharging curve figure (LiFePO4 LiFePO4/ lithium metal)；
Fig. 5 is the button electricity of the invention using the composite solid electrolyte film assembling in embodiment one under different multiplying
Cycle performance figure (the LiFePO4 LiFePO of (0.1C-1C)4/ lithium metal).
Specific embodiment
In order that the present invention can be more clearly and readily understood, below according to specific embodiments of the present invention to this hair
It is bright to be described in further detail.
Inorganic-organic hybrid solid electrolyte of the invention, includes the following components'mass percentage:
Polymeric binder 5%-60%
Lithium salts 10%-80% with ionic conductivity
Inorganic nanoparticles 10%-40%
The polymeric binder, including butadiene rubber (BR), nitrile rubber (NBR), butadiene-styrene rubber (SBR), hydrogenation fourth
One or more of nitrile rubber (HNBR), polyacrylonitrile (PAN), silica resin (polysiloxanes) or derivatives thereof.
The lithium salts with ionic conductivity is lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro boric acid
Lithium (LiBF4), lithium hexafluoro phosphate (LiPF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis- (trifluoromethane sulfonic acid) imine lithiums
(LiTFSi), three (trifluoromethane sulfonic acid) lithium methide (LiC (CF3SO2)3), di-oxalate lithium borate (LiBOB), difluoro (oxalic acid) boron
Sour lithium (LiBF2(C2O4)), bis- (fluorine sulphonyl) imine lithiums (LiFSi), difluorine oxalic acid boracic acid lithium (LiODFB) it is one such or
It is several.
The inorganic nanoparticles are active fast-ionic conductor or inert inorganic particle.
The activity fast-ionic conductor is Li7La3Zr2O12, LixLa2/3-xTi03, Li1+xAlxTi2-x(PO4)3, LiAlO2,
Li7-xLa3Zr2-xMxO12, Li10GeP2S12, yLi2S·(100-y)P2S5One or more of, wherein M=Ta, Nb, 0.25 < x
< 2,30≤y≤70.
The inert inorganic particle is SiO2、ZrO2、Al2O3、TiO2、BaTiO3One or more of.
The preparation method of above-mentioned inorganic-organic hybrid solid electrolyte, comprising the following steps:
Polymeric binder is added in decentralized medium according to the mass ratio of 1-4:30, is stirred at room temperature by step 1
It mixes, ultrasound is made into uniform polymer bonding agent solution；
Lithium salts and inorganic nanoparticles are added in the polymer bonding agent solution of step 1 preparation step 2, stirring
Uniform polymeric binder-lithium salts-inorganic nanoparticles slurry is obtained afterwards；
Polymeric binder-lithium salts-inorganic nanoparticles slurry obtained in step 2 is coated on polytetrafluoro by step 3
Solid-state electricity in vinyl plate, in an inert atmosphere by being dried in vacuo 12h at 50 DEG C, after sufficiently dry removal decentralized medium
Solution plasma membrane is removed from ptfe substrate, obtains solid electrolyte membrane.
The decentralized medium is carbonic ester, aromatic hydrocarbon, tertiary amine, one or more of ethers.Preferably methyl phenyl ethers anisole, first
One or more of benzene, tetrahydrofuran, triethylamine, glycol dimethyl ether.
Coating method is using blade coating, spraying, spin coating or electrostatic applications in the step 3.Coating method does not do specific limit
It is fixed, film uniformity is applied as long as can guarantee.
The solid lithium battery of above-mentioned inorganic-organic hybrid solid electrolyte assembling, including anode, cathode and between two
Solid electrolyte between person, anode include plus plate current-collecting body, positive electrode active materials, conductive agent, binder；Cathode includes lithium gold
One of category, lithium metal alloy.
The positive electrode active materials include the lithium metal oxide of stratiform, the material of spinel structure, polyanionic structure
One or more of material.
Preferably, lithium metal oxide includes LiMO2(M=Ni, Mn, Co) and tertiary cathode material LiNixMnyCozO2
(NMC) and LiNixCoyAlzO2(NCA)。
Preferably, polyanionic structure material includes LiFePO4 (LiFePO4), cobalt phosphate lithium (LiCoPO4), ferrosilite
Lithium (Li2FeSiO4)。
Preferably, polymeric binder is the butyronitrile rubber of weight average molecular weight (Mw) between 200000-500000g/mol
Glue；Nitrile rubber of the more preferably Mw between 300000-350000g/mol.
Preferably, the mass percentage content of nitrile rubber in the electrolyte is 5%-40%；Lithium salts is in the electrolyte
Mass percentage content is 30%-80%；The mass percentage content of inorganic nanoparticles in the electrolyte is 10%-30%.
More preferred, the mass percentage content of nitrile rubber in the electrolyte is 5%-20%；The quality of lithium salts in the electrolyte
Degree is 60%-80%；The mass percentage content of inorganic nanoparticles in the electrolyte is 10-20%.
Preferably, lithium salts is bis- (fluorine sulphonyl) imine lithiums (LiFSi).
Preferably, inorganic nanoparticles are α-Al2O3、β-Al2O3、γ-Al2O3One of or it is several；More preferably
, inorganic nanoparticles are γ-Al2O3。
Embodiment 1
A kind of preparation method of composite solid electrolyte is present embodiments provided, step includes:
Step 1: by bis- (fluorine sulphonyl) imine lithiums of 1g nitrile rubber, 7.2g, 20g tetrahydro under argon gas protection in glove box
THF solvent is mixed, and is stirred at room temperature, ultrasound is made into uniform nitrile rubber-lithium salt solution；
Step 2: by 1.8g inorganic nanoparticles γ-Al2O3It is added in nitrile rubber-lithium salt solution, is stirred at room temperature
It mixes, ultrasound obtains uniform nitrile rubber-lithium salts-inorganic nanoparticles slurry for 12 hours；
Step 3: nitrile rubber-lithium salts-inorganic nanoparticles slurry obtained in step 2 is existed by blade coating
On polyfluortetraethylene plate, by forced air drying 12h at 50 DEG C, after being sufficiently dried in vacuo 12h at further 50 DEG C, by it from substrate
The solid electrolyte membrane independently to form a film can be obtained in sur-face peeling.
Embodiment 2
A kind of preparation method of composite solid electrolyte is present embodiments provided, step includes:
Step 1: by bis- (fluorine sulphonyl) imine lithiums of 1g nitrile rubber, 3g, 10g tetrahydro furan under argon gas protection in glove box
Solvent of muttering is mixed, and is stirred at room temperature, ultrasound is made into uniform nitrile rubber-lithium salt solution；
Step 2: by 1g inorganic nanoparticles γ-Al2O3It is added in nitrile rubber-lithium salt solution, be stirred at room temperature,
Ultrasound obtains uniform nitrile rubber-lithium salts-inorganic nanoparticles slurry for 12 hours；
Step 3: nitrile rubber-lithium salts-inorganic nanoparticles slurry obtained in step 2 is existed by blade coating
On polyfluortetraethylene plate, by forced air drying 12h at 50 DEG C, after being sufficiently dried in vacuo 12h at further 50 DEG C, by it from substrate
The solid electrolyte membrane independently to form a film can be obtained in sur-face peeling.
Embodiment 3
A kind of preparation method of composite solid electrolyte is present embodiments provided, step includes:
Step 1: in glove box argon gas protection under by bis- (trifluoromethane sulfonic acid) imine lithiums of 1g nitrile rubber, 7.2g,
20g tetrahydrofuran solvent is mixed, and is stirred at room temperature, ultrasound is made into uniform nitrile rubber-lithium salt solution；
Step 2: by 1.8g inorganic nanoparticles γ-Al2O3It is added in nitrile rubber-lithium salt solution, is stirred at room temperature
It mixes, ultrasound obtains uniform nitrile rubber-lithium salts-inorganic nanoparticles slurry for 12 hours；
Step 3: nitrile rubber-lithium salts-inorganic nanoparticles slurry obtained in step 2 is existed by blade coating
On polyfluortetraethylene plate, by forced air drying 12h at 50 DEG C, after being sufficiently dried in vacuo 12h at further 50 DEG C, by it from substrate
The solid electrolyte membrane independently to form a film can be obtained in sur-face peeling.
Embodiment 4
A kind of preparation method of composite solid electrolyte is present embodiments provided, step includes:
Step 1: by bis- (trifluoromethane sulfonic acid) imine lithiums of 1g nitrile rubber, 3g, 10g under argon gas protection in glove box
Tetrahydrofuran solvent is mixed, and is stirred at room temperature, ultrasound is made into uniform nitrile rubber-lithium salt solution；
Step 2: by 1g inorganic nanoparticles γ-Al2O3It is added in nitrile rubber-lithium salt solution, be stirred at room temperature,
Ultrasound obtains uniform nitrile rubber-lithium salts-inorganic nanoparticles slurry for 12 hours；
Step 3: nitrile rubber-lithium salts-inorganic nanoparticles slurry obtained in step 2 is existed by blade coating
On polyfluortetraethylene plate, by forced air drying 12h at 50 DEG C, after being sufficiently dried in vacuo 12h at further 50 DEG C, by it from substrate
The solid electrolyte membrane independently to form a film can be obtained in sur-face peeling.
The ionic conductivity of solid electrolyte film is obtained in test above-described embodiment 1: above-mentioned solid electrolyte is clipped in
Among two panels stainless steel, it is placed in 2432 type battery cases.Ionic conductivity is measured using electrochemical alternate impedance spectrum, using public affairs
Formula: σ=L/ARb, wherein L is the thickness of electrolyte, and A is stainless steel substrates area, RbFor the impedance measured.It is obtained by measuring and calculation
Ionic conductivity when to the lithium salts at room temperature is 2.2 × 10-4S/cm, as shown in Figure 1.
Above-mentioned nitrile rubber-lithium salts-inorganic nanoparticles the dielectric film of gained is used for the assembling and charge and discharge of solid state lithium battery
The measurement of electric specific capacity.
Battery performance characterization
(1) preparation of positive plate
5g Kynoar (PVDF) is dissolved in 95g N-Methyl pyrrolidone (NMP), being made into mass fraction is
The solution of 5wt.%；8.34g PVDF/NMP solution, 9.2g LiFePO4 or cobalt acid lithium powder, 0.3g conductive black are passed through into ball
Mill is uniformly mixed into slurry；By above-mentioned resulting slurry with the blade coating of 100um on aluminium case, in air blast at subsequent 120 DEG C
In drying box overnight, it is cut by size spare.
(2) preparation of negative electrode tab: cathode is lithium metal；
Using lithium metal as cathode, cobalt acid lithium is anode, and electrolyte layer is nitrile rubber-lithium salts-inorganic nanoparticles electrolysis
Plasma membrane is assembled into button cell, carries out charge-discharge test with LAND charge-discharge test instrument.After tested, under the conditions of 25 DEG C, with this
Charging and discharging curve of the lithium ion battery of composite electrolyte assembling under the multiplying power of 0.1C is as shown in Figure 2.Under different multiplying
It is as shown in Figure 3 that specific capacity plays result, the results showed that, maximum electric discharge ratio of the solid state battery at 0.1C, 0.2C, 0.5C, 1C
Capacity is respectively 131mAh/g, 118mAh/g, 96mAh/g, 22mAh/g, as shown in Figure 3.
Using lithium metal as cathode, LiFePO4 is anode, and electrolyte layer is nitrile rubber-lithium salts-inorganic nanoparticles electricity
Plasma membrane is solved, button cell is assembled into, carries out charge-discharge test with LAND charge-discharge test instrument.After tested, under the conditions of 25 DEG C, with
Charging and discharging curve of the lithium ion battery of composite electrolyte assembling under the multiplying power of 0.1C is as shown in Figure 4.In different multiplying
Maximum specific discharge capacity under 0.1C, 0.2C, 0.5C, 1C is respectively 137mAh/g, 131mAh/g, 112mAh/g, 71mAh/g,
As shown in Figure 5.
Wherein table 1 is to be applied to button cell (cobalt acid lithium LiCoO using different composite electrolyte layer in the present invention2/ lithium gold
Belong to) moderate multiplying factor be 0.1C under maximum specific discharge capacity comparison.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Specific discharge capacity (mAh/g) | 131 | 119 | 108 | 97 |
Wherein table 2 be the present invention in using different polymeric binders, lithium salts, inorganic nanoparticles preparation it is inorganic-have
It is the maximum electric discharge ratio under 0.1C that machine composite solid electrolyte, which is applied to button cell (cobalt acid lithium LiCoO2/ lithium metal) moderate multiplying factor,
The comparison of capacity.
Table 2
Above-described embodiment only technical concept and feature to illustrate the invention, its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The Spirit Essence equivalence changes or modification done, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of inorganic-organic hybrid solid electrolyte, which is characterized in that include the following components'mass percentage:
Polymeric binder 5%-60%
Lithium salts 10%-80% with ionic conductivity
Inorganic nanoparticles 10%-40%
The polymeric binder, including the derivative polyacrylonitrile containing acrylonitrile, styrene or Gui Yang functional group, butyronitrile rubber
One or more of glue, butadiene rubber, butadiene-styrene rubber, hydrogenated nitrile-butadiene rubber, silica resin or derivatives thereof.
2. inorganic-organic hybrid solid electrolyte according to claim 1, which is characterized in that described that there is ionic conductivity
Lithium salts be lithium perchlorate LiClO4, hexafluoroarsenate lithium LiAsF6, LiBF4 LiBF4, lithium hexafluoro phosphate LiPF6, fluoroform
Base Sulfonic Lithium LiCF3SO3, bis- (trifluoromethane sulfonic acid) imine lithium LiTFSi, three (trifluoromethane sulfonic acid) lithium methide LiC
(CF3SO2)3, di-oxalate lithium borate LiBOB, difluoro (oxalic acid) lithium borate LiBF2(C2O4), bis- (fluorine sulphonyl) imine lithium LiFSi,
One of difluorine oxalic acid boracic acid lithium LiODFB is several.
3. inorganic-organic hybrid solid electrolyte according to claim 1, which is characterized in that the inorganic nanoparticles are
Active fast-ionic conductor or inert inorganic particle.
4. inorganic-organic hybrid solid electrolyte according to claim 3, which is characterized in that the activity fast-ionic conductor
For Li7La3Zr2O12, LixLa2/3-xTi03, Li1+xAlxTi2-x(PO4)3, LiAlO2, Li7-xLa3Zr2-xMxO12, Li10GeP2S12,
yLi2S·(100-y)P2S5One or more of, wherein M=Ta, Nb, 0.25 < x < 2,30≤y≤70.
5. inorganic-organic hybrid solid electrolyte according to claim 3, which is characterized in that the inert inorganic particle is
SiO2、ZrO2、Al2O3、TiO2、BaTiO3One or more of.
6. the preparation method of inorganic-organic hybrid solid electrolyte as described in claim 1, which is characterized in that including following step
It is rapid:
Polymeric binder is added in decentralized medium according to the mass ratio of 1-4:30, is stirred, surpasses at room temperature by step 1
Sound is made into uniform polymer bonding agent solution；
Lithium salts and inorganic nanoparticles are added in the polymer bonding agent solution of step 1 preparation, obtain after stirring by step 2
Obtain uniform polymeric binder-lithium salts-inorganic nanoparticles slurry；
Polymeric binder-lithium salts-inorganic nanoparticles slurry obtained in step 2 is coated on polytetrafluoroethylene (PTFE) by step 3
Solid electrolyte on plate, in an inert atmosphere by being dried in vacuo 12h at 50 DEG C, after sufficiently dry removal decentralized medium
Film is removed from ptfe substrate, obtains solid electrolyte membrane.
7. the preparation method of inorganic-organic hybrid solid electrolyte according to claim 6, which is characterized in that the dispersion
Medium is one or more of carbonic ester, aromatic hydrocarbon, tertiary amine, ethers.
8. the preparation method of inorganic-organic hybrid solid electrolyte according to claim 6, which is characterized in that the step
Coating method is using blade coating, spraying, spin coating or electrostatic applications in three.
9. the solid lithium battery of inorganic-organic hybrid solid electrolyte assembling as described in claim 1, which is characterized in that packet
Anode, cathode and the solid electrolyte to fall between are included, anode includes plus plate current-collecting body, positive electrode active materials, conduction
Agent, binder；Cathode includes one of lithium metal, lithium metal alloy.
10. the solid lithium battery of inorganic-organic hybrid solid electrolyte assembling according to claim 9, which is characterized in that
The positive electrode active materials include the lithium metal oxide of stratiform, the material of spinel structure, in polyanionic structure material
It is one or more of.
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