CN115425286A - Film based on nano sulfide solid electrolyte, preparation method and application - Google Patents
Film based on nano sulfide solid electrolyte, preparation method and application Download PDFInfo
- Publication number
- CN115425286A CN115425286A CN202211373448.9A CN202211373448A CN115425286A CN 115425286 A CN115425286 A CN 115425286A CN 202211373448 A CN202211373448 A CN 202211373448A CN 115425286 A CN115425286 A CN 115425286A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- sulfide solid
- less
- nano
- equal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000012442 inert solvent Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 59
- 239000010409 thin film Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000004793 Polystyrene Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002367 Polyisobutene Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 claims description 6
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229940007550 benzyl acetate Drugs 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229920000591 gum Polymers 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 56
- 239000007784 solid electrolyte Substances 0.000 abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000005476 size effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 22
- 239000011888 foil Substances 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000009694 cold isostatic pressing Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910012820 LiCoO Inorganic materials 0.000 description 8
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000010358 mechanical oscillation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a film based on a nano sulfide solid electrolyte, a preparation method and application, belonging to the technical field of solid electrolytes, wherein the preparation method comprises the following steps: (1) Adding 0.1-20 parts by weight of binder and 50-100 parts by weight of nano-sized sulfide solid electrolyte into an inert solvent, and uniformly mixing under a closed condition to obtain slurry; (2) And (2) coating the slurry obtained in the step (1) on a substrate, drying, and pressing to obtain the film based on the nano sulfide solid electrolyte. The preparation method takes the nano sulfide solid electrolyte, the inert solvent and the binder as raw materials, ensures the chemical stability of the nano sulfide solid electrolyte, and simultaneously utilizes the size effect among the raw materials and a specific preparation method to realize the preparation of the ultrathin sulfide electrolyte film with high density, low porosity, low impedance and high ionic conductivity.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a film based on a nano sulfide solid electrolyte, a preparation method and application.
Background
Compared with the conventional lithium ion battery, the all-solid-state lithium battery has the advantages of high safety and high energy density. Among the reported solid electrolytes, sulfide solid electrolytes have high ionic conductivity and can be densified by cold pressing at room temperature to generate a good interface, and thus, the solid electrolyte is a solid electrolyte with good application prospect. However, the sulfide solid electrolyte in the current all solid-state lithium battery is usually pressed into a sheet with a thickness of 1mm, and the thicker and heavier electrolyte layer makes the energy density of the all solid-state lithium battery not to be expected, so that the reduction of the thickness of the electrolyte layer is an important direction for increasing the energy density of the all solid-state lithium battery.
In order to obtain a thin and dense sulfide solid electrolyte membrane, researchers have adopted cold pressing, hot pressing, surface coating, introduction of a support, and the like. However, the thin films prepared by these methods are mostly in the thickness range of tens of micrometers or even hundreds of micrometers, and further reduction of the thin film thickness is difficult due to the large particle size of the sulfide solid electrolyte particles themselves.
The invention discloses a preparation method of a solid electrolyte film, which is disclosed in Chinese patent document with publication number CN110661032 A.A uniformly dispersed solid electrolyte solution is added into a uniformly dispersed flexible polymer solution, lithium salt is added after uniform mixing and uniform dispersion to obtain a solid electrolyte gel, and the solid electrolyte gel is cured and dried to obtain the solid electrolyte film, wherein the solid electrolyte is preferably garnet-type solid electrolyte; chinese patent document CN112909331A discloses a preparation method of an ultrathin sulfide electrolyte composite flexible film, which comprises the steps of mixing sulfide electrolyte, a solvent and a film-forming agent, and then adding a dispersing agent to obtain electrolyte slurry; and further, uniformly casting and dispersing the electrolyte slurry, drying and forming to obtain the ultrathin sulfide electrolyte composite flexible film. However, the thin film prepared in the above invention is thick, which affects the energy density of the battery.
Disclosure of Invention
The invention provides a preparation method of a film based on a nano sulfide solid electrolyte, which takes the nano sulfide solid electrolyte, an inert solvent and a binder as raw materials, and prepares the ultrathin sulfide electrolyte film with low impedance and high ionic conductivity through wet coating, and the sulfide electrolyte film can be further used for preparing an all-solid-state battery with high energy density.
The technical scheme is as follows:
a preparation method of a thin film based on a nano sulfide solid electrolyte comprises the following steps:
(1) Adding 0.1 to 20 parts by weight of binder and 50 to 100 parts by weight of nano-sized sulfide solid electrolyte into an inert solvent, and uniformly mixing under a closed condition to obtain slurry;
(2) And (2) coating the slurry obtained in the step (1) on a substrate, drying, and pressing to obtain the film based on the nano sulfide solid electrolyte.
The invention takes nano sulfide solid electrolyte, inert solvent and binder as raw materials, ensures the chemical stability of the nano sulfide solid electrolyte, and simultaneously utilizes the size effect among the raw materials and a specific preparation method to realize the preparation of the ultrathin sulfide electrolyte film with high density, low porosity, low impedance and high ionic conductivity.
Preferably, the binder is 0.5 to 5 parts by weight, and the nano-sized sulfide solid electrolyte is 95 to 99.5 parts by weight. The sulfide electrolyte thin film prepared in the preferable range has better electrochemical performance.
The binder is a copolymer of one or more monomers of polytetrafluoroethylene, polymethyl methacrylate, polyisobutylene, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyethylene glycol, polyethylene oxide, polyacrylic acid, gum, guar gum, carboxymethyl cellulose, butadiene rubber, styrene butadiene rubber, nitrile butadiene rubber, polyvinyl alcohol, polyacrylonitrile, butyl acrylate and polyvinyl butyral.
Preferably, the particle size of the nanometer sulfide solid electrolyte is 10 to 500 nm.
The nano-sized sulfide solid electrolyte is one or a mixture of sulfide solid electrolytes with general formulas of a formula (I), a formula (II) and a formula (III);
(100-x-y) Li 2 S·xP 2 S 5 ·yM m N n （I）
in the formula (I), 0 is more than or equal to x and less than 100,0 is more than or equal to y and less than 100,0 is more than x + y and less than 100,0 is more than or equal to m and less than 4,0 is more than or equal to N and 6,M is Ge, si, sn or Sb, and N is Se, O, cl, br or I;
Li 10±l Ge 1-g G g P 2-q Q q S 12-w W w （II）
in the formula (II), l is more than or equal to 0 and less than 1,0 and less than or equal to g and less than or equal to 1,0 and less than or equal to Q and less than 2,0 and less than or equal to W and less than 1,G is Si or Sn, Q is Sb, as or Ti, and W is O, se, F, cl, br or I;
Li 6±l P 1-e E e S 5-r±t R r X 1±t （Ⅲ）
in the formula (III), l is more than or equal to 0 and less than 1,0 and less than e and less than 1,0 and less than R and less than 2,0 and less than t and less than 1,E is Ge, si, sn or Sb, R is O, se, F, cl, br or I, and X is F, cl, br or I.
The inert solvent is one or a mixture of more of toluene, chlorobenzene, xylene, dimethyl carbonate, N-methylformamide, N-hexane, glyme, dibutyl ether, ethanol, 1,2-ethylenediamine, dichloroethane, dibromomethane, anisole, triethyl phosphate, dimethyl sulfoxide, dichloromethane, 1,2-ethanedithiol, acetonitrile, tetrahydrofuran, isoamyl ether, butyl butyrate, isopropyl ether, N-heptane, hexene, ethyl acetate and benzyl acetate. The inert solvent and the sulfide electrolyte have weaker reactivity and are generally low-polarity solvents, nano sulfide solid electrolyte particles with smaller sizes are dispersed in the inert solvent more uniformly, and the thickness of the prepared electrolyte film is lower.
Preferably, the mixing method is one or more of mechanical stirring, mechanical oscillation, ultrasonic dispersion, ball milling, roll milling and agate mortar grinding, and the mixing time is 0.1 to 12 hours.
In the step (2), the substrate includes, but is not limited to, copper foil, aluminum foil, glass plate, steel plate, PET, PE substrate, or an extended product coated on the surface of the above-mentioned material.
Preferably, the slurry of step (1) is coated on a substrate using a coater.
In the step (2), the drying method is vacuum drying or forced air drying, the drying temperature is 10-200 ℃, and the drying time is 0.1-48 hours.
And (2) pressing by using an isostatic press or a press and the like, wherein the pressure is 50 to 600Mpa, and the pressing temperature is 20 to 100 ℃.
The invention also provides the sulfide solid electrolyte film prepared by the preparation method of the film based on the nano sulfide solid electrolyte, and the solid content of the sulfide solid electrolyte film is 80-99.9%.
Preferably, the thickness of the sulfide solid electrolyte film is 1 to 40 micrometers, and the impedance value is 0.1 to 10 omega mm -1 (ii) a The ionic conductivity is 0.1 to 5 mS cm -1 。
The invention also provides an application of the sulfide solid electrolyte film in an all-solid-state battery, in particular to an all-solid-state lithium battery, which comprises the following components: a positive electrode, a negative electrode and the film based on the nano-sulfide solid electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for thinning a nano sulfide solid electrolyte by wet coating, which is characterized in that nano sulfide solid electrolyte particles and a high-strength binder are dispersed into an inert solvent to obtain mixed slurry, and the mixed slurry is coated on a substrate to obtain a uniform and compact ultrathin sulfide solid electrolyte film with low impedance value and high ionic conductivity.
(2) The preparation process of the sulfide solid electrolyte film provided by the invention is simple, high in efficiency and convenient for large-scale production, and the sulfide solid electrolyte film is used as an electrolyte layer, so that the thickness and weight of the electrolyte layer are greatly reduced, and the preparation of a high-energy-density all-solid-state lithium battery can be realized.
Drawings
FIG. 1 shows Li in example 1 5.4 PS 4.4 Cl 1.2 Br 0.4 Scanning electron microscope cross section of the sulfide solid electrolyte film.
FIG. 2 shows Li in example 1 5.4 PS 4.4 Cl 1.2 Br 0.4 And (3) an alternating current impedance spectrum of the sulfide solid electrolyte film.
FIG. 3 is LiCoO in example 1 2 /Li 5.4 PS 4.4 Cl 1.2 Br 0.4 Cycle performance plot of thin film/Li battery.
FIG. 4 is LiCoO in example 1 2 /Li 5.4 PS 4.4 Cl 1.2 Br 0.4 Charge and discharge curves for thin film/Li batteries.
Detailed Description
The invention will be further elucidated with reference to the embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
The particle size distribution of the raw material nano-sized sulfide solid electrolyte in examples 1 to 13 was in the range of 100 to 500 nm.
Example 1
(1) In a glove box, 97 parts by weight of nanoscale Li 5.4 PS 4.4 Cl 1.2 Br 0.4 Dispersing electrolyte and 3 parts by weight of methyl methacrylate/n-butyl acrylate (MMA/nBA) copolymer (the synthesis method is detailed in Mark W. Urban et al. Key-and-lock comfort selection-polymers, doi 10.1126/science. Aat 2975) into 100 parts by weight of toluene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) drying in vacuum for 12 hours, and carrying out cold isostatic pressing at 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 5.4 PS 4.4 Cl 1.2 Br 0.4 The sulfide solid electrolyte film is about 5 mu m thick, compact and has a cross section as shown in a scanning electron microscope figure 1; the room temperature impedance value is 0.3 omega.mm -1 Ion conductance of3333 mS, calculated to obtain an ionic conductivity of 2.12 mS cm -1 The AC impedance spectrum is shown in FIG. 2.
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 70% by mass, the electrolyte film prepared in this example was an electrolyte layer, and metallic lithium was a negative electrode, and an all-solid battery was assembled; the battery can stably circulate for 100 circles under 0.1C, the capacity retention rate is 80.3 percent, the battery cycle performance is shown in figure 3, and the charge-discharge curve is shown in figure 4.
Example 2
(1) In a glove box, 99 parts by weight of nanoscale Li 6 PS 5 Dispersing a Cl electrolyte and 1 part by weight of Polyisobutylene (PIB) into 100 parts by weight of dimethylbenzene, and mechanically stirring and mixing for 2 hours in a closed container to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And C, drying in vacuum for 12 hours, and carrying out cold isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 6 PS 5 A Cl sulfide solid electrolyte thin film with a thickness of about 4 μm; the impedance value at room temperature is 1.2 omega.mm -1 The ionic conductivity is 833 mS which is calculated to be 0.42 mS cm -1 。
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the lithium-magnesium alloy is a cathode, and the all-solid-state battery is assembled, wherein the battery can stably circulate for 100 circles at 0.1 ℃, and the capacity retention rate is 80.4%.
Example 3
(1) In a glove box, 95 parts by weight of nanoscale Li 10 GeP 2 S 12 Dispersing electrolyte and 5 parts by weight of carboxymethyl cellulose (CMC) into 100 parts by weight of toluene, and mechanically stirring and mixing the mixture in a closed container for 25 minutes to obtain uniform slurry;
(2) Applying the above slurry to a substrate in an adjustable mannerMachine coated on aluminum foil, transferred to vacuum oven 80 o And (C) vacuum drying for 12 hours, and carrying out hot isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 10 GeP 2 S 12 A sulfide solid electrolyte thin film having a thickness of about 8 μm; the impedance value at room temperature is 0.5 omega.mm -1 The ionic conductivity is 2000 mS, and the ionic conductivity is calculated to be 2.04 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material, is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, wherein the battery can stably circulate for 150 circles at 0.2 ℃, and the capacity retention rate is 90.41%.
Example 4
(1) In a glove box, 99 parts by weight of nanoscale Li 7 P 3 S 11 Dispersing electrolyte and 1 part by weight of polyvinylidene fluoride (PVDF) into 100 parts by weight of tetrahydrofuran, and ball-milling and mixing for 2 hours in a closed container to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) drying in vacuum for 12 hours, and carrying out cold isostatic pressing at 100MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 7 P 3 S 11 A sulfide solid electrolyte thin film having a thickness of about 4.5 μm; the impedance value at room temperature is 0.5 omega.mm -1 The ionic conductivity is 2000 mS, and the ionic conductivity is calculated to be 1.15 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material and is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, can stably circulate for 100 circles at 0.1 ℃ and has the capacity retention rate of 85.3%.
Example 5
(1) In a glove box, 99 parts by weight of nanoscale Li 3 PS 4 Dispersing the electrolyte I and 1 part by weight of Nitrile Butadiene Rubber (NBR) into 100 parts by weight of ethyl acetate, and performing ball milling and mixing for 2 hours in a closed container to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) vacuum drying for 12 hours, and hot isostatic pressing for 300MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 3 PS 4 I, a sulfide solid electrolyte film with the thickness of about 8 mu m; the room temperature impedance value is 0.42 omega.mm -1 The ionic conductivity is 2381 mS, and the ionic conductivity is calculated to be 2.43 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material and is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, wherein the battery can stably circulate for 300 circles under 1C, and the capacity retention rate is 86.98%.
Example 6
(1) In a glove box, 99 parts by weight of nanoscale Li 6 PS 5 Dispersing Cl electrolyte and 1 part by weight of Styrene Butadiene Rubber (SBR) into 100 parts by weight of butyl butyrate, and roll-milling and mixing for 2 hours in a closed container to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) drying the film for 12 hours in vacuum, and carrying out cold isostatic pressing on the film based on the nano sulfide solid electrolyte after 200 MPa.
(3) Performance testing and Battery Assembly
Li obtained in this example 6 PS 5 A Cl sulfide solid electrolyte thin film with a thickness of about 5 μm; the room temperature impedance value is 1.5 omega mm -1 The ionic conductivity is 667 mS, and the ionic conductivity is calculated to be 0.42 mS cm -1 。
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 70% by mass, the electrolyte film prepared in the embodiment is an electrolyte layer, the lithium boron alloy is a cathode, and the all-solid-state battery is assembled, can stably circulate for 150 circles at 0.1 ℃, and has a capacity retention rate of 86.17%.
Example 7
(1) In a glove box, 99 parts by weight of nanoscale Li 10 GeP 2 S 12 Dispersing electrolyte and 1 part by weight of Polyisobutylene (PIB) into 100 parts by weight of n-heptane, and roll-milling in a closed container for 2 hours to obtain uniform slurry;
(2) Coating the slurry on a carbon-coated aluminum foil by using an adjustable coating machine, and transferring the carbon-coated aluminum foil to a vacuum oven 80 o And C, drying in vacuum for 12 hours, and carrying out cold isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 10 GeP 2 S 12 A sulfide solid electrolyte thin film having a thickness of about 15 μm; the room temperature impedance value of the film is 0.7 omega.mm -1 The ionic conductivity is 1429 mS, which is calculated to be 2.73 mS cm -1 。
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, can stably circulate for 400 circles at 0.2 ℃, and has a capacity retention rate of 89.2%.
Example 8
(1) In a glove box, 98 parts by weight of nanoscale Li 5.4 PS 4.4 Cl 1.6 Electrolyte and 2 parts by weight of methyl methacrylate/propyleneDispersing an olefine acid n-butyl ester (MMA/nBA) copolymer into 100 parts by weight of toluene, and performing roll milling and mixing in a closed container for 2 hours to obtain uniform slurry;
(2) Coating the slurry on a copper foil by using an adjustable coating machine, and transferring the copper foil to a vacuum oven 80 o And (C) drying in vacuum for 12 hours, and carrying out cold isostatic pressing at 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 5.4 PS 4.4 Cl 1.6 A sulfide solid electrolyte thin film having a thickness of about 30 μm; the impedance value at room temperature is 5.1 omega.mm -1 The ionic conductivity is 196 mS, and the ionic conductivity is calculated to be 0.75 mS cm -1 。
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 The electrolyte thin film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled and can be stably cycled for 500 circles at 0.1 ℃, and the capacity retention rate is 89.11%.
Example 9
(1) In a glove box, 95 parts by weight of nanoscale Li 7 P 2 S 8 Dispersing the electrolyte I and 5 parts by weight of Polyisobutylene (PIB) into 100 parts by weight of dimethylbenzene, and grinding and mixing the mixture in an agate mortar in a closed container for 1 hour to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) drying in vacuum for 12 hours, and carrying out cold isostatic pressing at 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 7 P 2 S 8 I, a sulfide solid electrolyte film with the thickness of about 5 mu m; the impedance value at room temperature is 2.1 omega.mm -1 The ionic conductivity is 476 mS, and the ionic conductivity is calculated to be 0.3 mS cm -1 。
With LiCoO 2 Is a positive electrode active material, and is a composite positive electrode materialMedium LiCoO 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, can stably circulate for 150 circles under 1C, and has a capacity retention rate of 87.3%.
Example 10
(1) In a glove box, 99 parts by weight of nanoscale Li 5.5 PS 4.5 Cl 1.5 Dispersing electrolyte and 1 part by weight of carboxymethyl cellulose (CMC) into 100 parts by weight of toluene, and grinding and mixing the materials in an agate mortar in a closed container for 1 hour to obtain uniform slurry;
(2) Coating the slurry on a copper foil by using an adjustable coating machine, and transferring the copper foil to a vacuum oven 80 o And (C) drying in vacuum for 12 hours, and carrying out cold isostatic pressing at 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 5.5 PS 4.5 Cl 1.5 A sulfide solid electrolyte thin film having a thickness of about 3 μm; the room temperature resistance value of the film is 0.23 omega.mm -1 The ionic conductivity is 4348 mS and the ionic conductivity is 1.66 mS cm -1 。
With LiCoO 2 LiCoO as positive electrode active material in composite positive electrode material 2 The electrolyte thin film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled and can stably circulate for 80 circles at 0.1 ℃ and has a capacity retention rate of 82.3%.
Example 11
(1) In a glove box, 99 parts by weight of nanoscale Li 5.4 PS 4.4 Cl 1.2 Br 0.4 Dispersing electrolyte and 1 part by weight of polyvinylidene fluoride (PVDF) into 100 parts by weight of benzyl acetate, and mechanically stirring and mixing in a closed container for 25 minutes to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) vacuum drying for 12 hours, and carrying out hot isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 5.4 PS 4.4 Cl 1.2 Br 0.4 A sulfide solid electrolyte thin film having a thickness of about 7 μm; the impedance value at room temperature is 0.3 omega.mm -1 The ionic conductivity is 3333 mS and the ionic conductivity is 2.97 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material and is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, can stably circulate for 200 circles at 0.5 ℃ and has a capacity retention rate of 83.4%.
Example 12
(1) In a glove box, 99 parts by weight of nanoscale 75Li 2 S•25P 2 S 5 Dispersing an electrolyte and 1 part by weight of Nitrile Butadiene Rubber (NBR) into 100 parts by weight of ethyl acetate, and mechanically stirring and mixing for 25 minutes in a closed container to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And C, drying in vacuum for 12 hours, and carrying out cold isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
75Li prepared in this example 2 S•25P 2 S 5 A sulfide solid electrolyte thin film having a thickness of about 12 μm; the impedance value at room temperature is 0.8 omega.mm -1 The ionic conductivity is 1250 mS and the ionic conductivity is 1.91 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material and is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 70% by mass, the electrolyte film prepared in the embodiment is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled, can stably circulate for 100 circles at 0.3 ℃, and has the capacity retention rate of 82.3%。
Example 13
(1) In a glove box, 99.5 parts by weight of nanoscale Li 6 PS 5 Dispersing Cl electrolyte and 0.5 weight part of polyvinylidene fluoride (PVDF) into 100 weight parts of anisole, and mechanically stirring and mixing in a closed container for 25 minutes to obtain uniform slurry;
(2) Coating the slurry on an aluminum foil by using an adjustable coating machine, and transferring the aluminum foil to a vacuum oven 80 o And (C) vacuum drying for 12 hours, and carrying out hot isostatic pressing for 200MPa to obtain the film based on the nano sulfide solid electrolyte.
(3) Performance testing and Battery Assembly
Li obtained in this example 6 PS 5 A Cl sulfide solid electrolyte thin film with a thickness of about 4 μm; the room temperature impedance value of the film is 0.2 omega.mm -1 The ionic conductivity is 3571 mS and the ionic conductivity is 1.82 mS cm -1 。
With LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode active material and is compounded with LiNi in a positive electrode material 0.6 Co 0.2 Mn 0.2 O 2 The electrolyte film prepared in the embodiment is an electrolyte layer, the lithium boron alloy is a cathode, and the all-solid-state battery is assembled, wherein the electrolyte film is 70% in mass percentage, can stably circulate for 50 circles at 0.2 ℃, and has a capacity retention rate of 92.4%.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a film based on a nano sulfide solid electrolyte is characterized by comprising the following steps:
(1) Adding 0.1-20 parts by weight of binder and 50-100 parts by weight of nano-sized sulfide solid electrolyte into an inert solvent, and uniformly mixing under a closed condition to obtain slurry;
(2) And (2) coating the slurry obtained in the step (1) on a substrate, drying, and pressing to obtain the film based on the nano sulfide solid electrolyte.
2. The method for preparing a nano-sulfide solid electrolyte-based film according to claim 1, wherein the binder is 0.5 to 5 parts by weight, and the nano-sized sulfide solid electrolyte is 95 to 99.5 parts by weight.
3. The method of claim 1, wherein the binder is a copolymer of one or more monomers selected from the group consisting of polytetrafluoroethylene, polymethyl methacrylate, polyisobutylene, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyethylene glycol, polyethylene oxide, polyacrylic acid, gum, guar gum, carboxymethyl cellulose, butadiene rubber, styrene butadiene rubber, nitrile butadiene rubber, polyvinyl alcohol, polyacrylonitrile, butyl acrylate, and polyvinyl butyral.
4. The method for preparing the nano-sulfide solid electrolyte-based film according to claim 1, wherein the nano-size sulfide solid electrolyte has a particle size of 10 to 500 nm.
5. The method for preparing the nano sulfide solid electrolyte-based thin film according to claim 1, wherein the nano sulfide solid electrolyte is one or a mixture of several of sulfide solid electrolytes with general formulas of formula (I), formula (II) or formula (III);
(100-x-y) Li 2 S·xP 2 S 5 ·yM m N n （I）
in the formula (I), 0 is more than or equal to x and less than 100,0 is more than or equal to y and less than 100,0 is more than x + y and less than 100,0 is more than or equal to m and less than 4,0 is more than or equal to N and 6,M is Ge, si, sn or Sb, and N is Se, O, cl, br or I;
Li 10±l Ge 1-g G g P 2-q Q q S 12-w W w （II）
in the formula (II), l is more than or equal to 0 and less than 1,0 and less than or equal to g and less than or equal to 1,0 and less than or equal to Q and less than 2,0 and less than or equal to W and less than 1,G is Si or Sn, Q is Sb, as or Ti, and W is O, se, F, cl, br or I;
Li 6±l P 1-e E e S 5-r±t R r X 1±t （Ⅲ）
in the formula (III), l is more than or equal to 0 and less than 1,0 and less than e and less than 1,0 and less than R and less than 1,0 and less than t and less than 1,E is Ge, si, sn or Sb, R is O, se, F, cl, br or I, and X is F, cl, br or I.
6. The method of claim 1, wherein the inert solvent is one or more selected from the group consisting of toluene, chlorobenzene, xylene, dimethyl carbonate, N-methylformamide, N-hexane, glyme, dibutyl ether, ethanol, 1,2-ethylenediamine, dichloroethane, dibromomethane, anisole, triethyl phosphate, dimethyl sulfoxide, dichloromethane, 1,2-ethanedithiol, acetonitrile, tetrahydrofuran, isoamyl ether, butyl butyrate, isopropyl ether, N-heptane, hexene, ethyl acetate, and benzyl acetate.
7. The method of preparing a nano sulfide solid electrolyte-based thin film according to claim 1, wherein the slurry of step (1) is coated on a substrate using a coater.
8. The sulfide solid electrolyte thin film manufactured by the method for manufacturing a nano sulfide solid electrolyte thin film according to any one of claims 1 to 7.
9. The sulfide solid electrolyte membrane according to claim 8, wherein the thickness of the sulfide solid electrolyte membrane is 1 to 40 μm, and the impedance value is 0.1 to 10 Ω mm -1 (ii) a The ionic conductivity is 0.1-5 mS cm -1 。
10. Use of the sulfide solid electrolyte thin film according to claim 8 in an all-solid battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211373448.9A CN115425286A (en) | 2022-11-04 | 2022-11-04 | Film based on nano sulfide solid electrolyte, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211373448.9A CN115425286A (en) | 2022-11-04 | 2022-11-04 | Film based on nano sulfide solid electrolyte, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115425286A true CN115425286A (en) | 2022-12-02 |
Family
ID=84207847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211373448.9A Pending CN115425286A (en) | 2022-11-04 | 2022-11-04 | Film based on nano sulfide solid electrolyte, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115425286A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018194248A2 (en) * | 2017-04-17 | 2018-10-25 | 인천대학교 산학협력단 | Organic additive coating method for improving interface stability of lithium secondary battery positive electrode material |
| CN109786845A (en) * | 2019-01-23 | 2019-05-21 | 蜂巢能源科技有限公司 | Sulfide electrolyte slurry and its preparation method and application |
| JPWO2018164050A1 (en) * | 2017-03-07 | 2019-11-07 | 富士フイルム株式会社 | Inorganic solid electrolyte material, and slurry using the same, solid electrolyte membrane for all solid secondary battery, solid electrolyte sheet for all solid secondary battery, positive electrode active material film for all solid secondary battery, for all solid secondary battery Negative electrode active material film, electrode sheet for all-solid-state secondary battery, all-solid-state secondary battery, and method for producing all-solid-state secondary battery |
| CN111244532A (en) * | 2020-03-23 | 2020-06-05 | 上海汽车集团股份有限公司 | Three-dimensional inorganic polymer composite solid electrolyte and ternary solid lithium battery |
| CN112366288A (en) * | 2020-10-30 | 2021-02-12 | 蜂巢能源科技(无锡)有限公司 | Electrolyte membrane, preparation method and application thereof |
| CN112909329A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Electrode-supported ultrathin sulfide electrolyte layer and preparation method and application thereof |
| CN112909330A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Self-supporting ultrathin sulfide electrolyte sheet, and preparation method and application thereof |
| CN112909331A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide electrolyte composite flexible film and preparation method and application thereof |
| CN113782824A (en) * | 2021-08-20 | 2021-12-10 | 蜂巢能源科技有限公司 | Sulfide electrolyte membrane and preparation method and application thereof |
| CN114256499A (en) * | 2021-12-23 | 2022-03-29 | 中南大学 | Preparation method of all-solid-state battery with lithium-supplement sulfide solid electrolyte membrane |
| CN114335700A (en) * | 2022-01-13 | 2022-04-12 | 湖南立方新能源科技有限责任公司 | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method |
| CN114824273A (en) * | 2022-04-15 | 2022-07-29 | 广东马车动力科技有限公司 | Sulfide composite solid electrolyte membrane, preparation method thereof and solid battery |
| CN115133117A (en) * | 2022-09-02 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | Nanometer-sized sulfide solid electrolyte material and preparation method thereof |
-
2022
- 2022-11-04 CN CN202211373448.9A patent/CN115425286A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2018164050A1 (en) * | 2017-03-07 | 2019-11-07 | 富士フイルム株式会社 | Inorganic solid electrolyte material, and slurry using the same, solid electrolyte membrane for all solid secondary battery, solid electrolyte sheet for all solid secondary battery, positive electrode active material film for all solid secondary battery, for all solid secondary battery Negative electrode active material film, electrode sheet for all-solid-state secondary battery, all-solid-state secondary battery, and method for producing all-solid-state secondary battery |
| WO2018194248A2 (en) * | 2017-04-17 | 2018-10-25 | 인천대학교 산학협력단 | Organic additive coating method for improving interface stability of lithium secondary battery positive electrode material |
| CN109786845A (en) * | 2019-01-23 | 2019-05-21 | 蜂巢能源科技有限公司 | Sulfide electrolyte slurry and its preparation method and application |
| CN112909330A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Self-supporting ultrathin sulfide electrolyte sheet, and preparation method and application thereof |
| CN112909331A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide electrolyte composite flexible film and preparation method and application thereof |
| CN112909329A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Electrode-supported ultrathin sulfide electrolyte layer and preparation method and application thereof |
| CN111244532A (en) * | 2020-03-23 | 2020-06-05 | 上海汽车集团股份有限公司 | Three-dimensional inorganic polymer composite solid electrolyte and ternary solid lithium battery |
| CN112366288A (en) * | 2020-10-30 | 2021-02-12 | 蜂巢能源科技(无锡)有限公司 | Electrolyte membrane, preparation method and application thereof |
| CN113782824A (en) * | 2021-08-20 | 2021-12-10 | 蜂巢能源科技有限公司 | Sulfide electrolyte membrane and preparation method and application thereof |
| CN114256499A (en) * | 2021-12-23 | 2022-03-29 | 中南大学 | Preparation method of all-solid-state battery with lithium-supplement sulfide solid electrolyte membrane |
| CN114335700A (en) * | 2022-01-13 | 2022-04-12 | 湖南立方新能源科技有限责任公司 | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method |
| CN114824273A (en) * | 2022-04-15 | 2022-07-29 | 广东马车动力科技有限公司 | Sulfide composite solid electrolyte membrane, preparation method thereof and solid battery |
| CN115133117A (en) * | 2022-09-02 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | Nanometer-sized sulfide solid electrolyte material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张锦等: "墨水涂覆法制备硫化物全固态锂离子电池", 《中南大学学报(自然科学版)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4040546A1 (en) | Lithium-supplementing negative electrode piece, preparation method therefor and lithium ion battery | |
| CN112420986B (en) | Method for preparing positive and negative pole pieces of lithium battery by dry method | |
| CN112599928A (en) | Composite diaphragm with lithium supplementing effect, preparation method thereof and lithium ion battery | |
| CN112751029A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN112209362B (en) | Method for activating carbon fluoride by plasma induction and preparation of lithium primary battery | |
| CN111933892B (en) | Negative plate, preparation method thereof and lithium ion secondary battery comprising negative plate | |
| CN110600680A (en) | Positive electrode slurry, positive plate comprising positive electrode slurry and lithium ion battery | |
| CN115440931A (en) | Lithium ion battery electrode plate and preparation method thereof | |
| CN115621416A (en) | Negative electrode with air-stable negative electrode prelithiation interface layer and preparation method | |
| CN111244373A (en) | Feedback type lithium ion battery diaphragm material and preparation and application thereof | |
| CN113013382B (en) | Method for preparing solid-state battery electrode by dry method, solid-state battery electrode and solid-state battery | |
| CN114256499A (en) | Preparation method of all-solid-state battery with lithium-supplement sulfide solid electrolyte membrane | |
| CN110600684A (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN117497835A (en) | Solid-state battery cell, preparation method thereof and solid-state battery | |
| CN117059885A (en) | Solid electrolyte membrane and preparation method and application thereof | |
| CN116799210A (en) | Composite lithium supplementing material and preparation method thereof, lithium supplementing coating and preparation method thereof, and lithium battery | |
| CN115425286A (en) | Film based on nano sulfide solid electrolyte, preparation method and application | |
| CN116190767A (en) | Sulfide solid electrolyte film based on self-healing binder, preparation method thereof and all-solid-state lithium battery | |
| CN114512710A (en) | Coated sulfide solid electrolyte material and preparation method and application thereof | |
| CN113851786A (en) | Pre-lithiation composite diaphragm and preparation method thereof | |
| CN114122358A (en) | Quick-filling graphite composite material and preparation method thereof | |
| CN115347149A (en) | Ultra-dispersed nano composite conductive adhesive and preparation method and application thereof | |
| CN109560280B (en) | Nano tin-molybdenum disulfide compound anode material and preparation method and application thereof | |
| CN113471398A (en) | Electrode slurry based on halide solid electrolyte, solid electrode and all-solid-state battery | |
| CN112456536A (en) | Solid electrolyte material, fluorine ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221202 |