CN117458012A - Sulfide solid electrolyte membrane, preparation method thereof and all-solid alkali metal ion battery - Google Patents
Sulfide solid electrolyte membrane, preparation method thereof and all-solid alkali metal ion battery Download PDFInfo
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- CN117458012A CN117458012A CN202311799872.4A CN202311799872A CN117458012A CN 117458012 A CN117458012 A CN 117458012A CN 202311799872 A CN202311799872 A CN 202311799872A CN 117458012 A CN117458012 A CN 117458012A
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- solid electrolyte
- sulfide
- electrolyte membrane
- sulfide solid
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- 239000012528 membrane Substances 0.000 title claims abstract description 198
- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 172
- 239000007787 solid Substances 0.000 title claims abstract description 80
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 28
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000002245 particle Substances 0.000 claims abstract description 133
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 60
- 239000011230 binding agent Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 13
- 238000007731 hot pressing Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 abstract description 24
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 86
- 229910001416 lithium ion Inorganic materials 0.000 description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 45
- 239000003792 electrolyte Substances 0.000 description 43
- 230000014759 maintenance of location Effects 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 description 30
- 229910052744 lithium Inorganic materials 0.000 description 26
- 239000000843 powder Substances 0.000 description 23
- 239000007784 solid electrolyte Substances 0.000 description 20
- 229910052717 sulfur Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000006872 improvement Effects 0.000 description 12
- -1 lithium carboxylate Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 6
- 229910012820 LiCoO Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 230000037427 ion transport Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical group [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910012465 LiTi Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229940065287 selenium compound Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- HIDOPYNXWKECHK-UHFFFAOYSA-L P(=O)([O-])([O-])F.[Fe+2].[Na+] Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Na+] HIDOPYNXWKECHK-UHFFFAOYSA-L 0.000 description 1
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HGBJDVIOLUMVIS-UHFFFAOYSA-N [Co]=O.[Na] Chemical compound [Co]=O.[Na] HGBJDVIOLUMVIS-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
- H01M2300/0097—Composites in the form of layered products, e.g. coatings with adhesive layers
Abstract
The invention provides a sulfide solid electrolyte membrane, a preparation method thereof and an all-solid alkali metal ion battery, and belongs to the technical field of all-solid batteries. The sulfide solid electrolyte membrane is composed of sulfide particles containing a polymer coating layer, the chemical composition of the sulfide particles containing the polymer coating layer is [ E ] m M n S o ] C α O β S γ H δ N ζ E a . Compared with the sulfide solid electrolyte membrane in the related art, the sulfide solid electrolyte membrane has excellent ionic conductivity, mechanical property and wide electrochemical window, has good interface stability and is not in positive contact with high voltageThe polar active material has chemical/electrochemical side reaction, so that the electrochemical performance of the high-voltage all-solid-state alkali metal ion battery can be obviously improved; moreover, the sulfide solid electrolyte membrane has excellent self-repairing performance, can resist the stress caused by the volume expansion of the electrode, and keeps the structural integrity of the sulfide solid electrolyte membrane.
Description
Technical Field
The invention belongs to the technical field of all-solid-state batteries, and particularly relates to a sulfide solid electrolyte membrane, a preparation method thereof and an all-solid-state alkali metal ion battery.
Background
The current commercial alkali metal ion battery is a liquid lithium ion battery adopting liquid organic electrolyte, but the liquid organic electrolyte is inflammable and volatile, and under the abuse conditions of overcharge, impact and the like, the liquid battery is easy to have severe combustion and other safety accidents. In contrast, all-solid-state alkali metal ion batteries using solid electrolyte membranes have higher safety while enabling higher energy densities to be achieved with matched alkali metal electrodes. Therefore, the development of all-solid-state alkali metal ion batteries as next-generation energy storage devices has received great attention in academia and industry.
The solid electrolyte membrane of all-solid alkali metal ion batteries is diverse in kinds, and among them, sulfide solid electrolyte membranes having high ionic conductivity and easy workability, which can be brought into close contact with active materials by cold pressing, achieve low interface resistance, are considered to be the most potential solid electrolyte membranes. However, currently, sulfide solid electrolyte membranes (in which sulfide solid electrolytes such as Li 3 PS 4 、Li 6 PS 5 Cl、Li 10 GeP 2 S 12 Etc.) is very poor in compatibility with commercial high-voltage cathode materials (e.g., lithium cobaltate, ternary high-nickel cathode materials, lithium nickel manganate, etc.), due to the easy Li removal of sulfide solid electrolyte membranes at high voltages + Cause S 2- Oxidation occurs to generate a series of high interface impedance products such as simple substance S, and ion transport on an anode/electrolyte membrane interface is severely restricted. Heretofore, a sulfide solid electrolyte membrane having low cost, excellent mechanical properties and high voltage resistance, high ion conductivity (in which the binder content<10 wt%) remains a challenge. This is in combination with the intrinsic thermodynamic instability of the sulfide solid state electrolyte particles andthe lack of a binder system that is compatible with sulfide solid state electrolytes is highly relevant.
In view of the above problems, many studies have been made in the related art. For example, patent application document 202211153228.5 discloses a lithium ion conductive adhesive, a preparation method thereof, a sulfide electrolyte membrane, a preparation method thereof and a lithium battery, wherein the adhesive of the sulfide solid electrolyte membrane is a styrene-butadiene-styrene block copolymer grafted with lithium carboxylate, has strong viscosity, and can improve the ion conductivity of the sulfide solid electrolyte membrane. Patent application 202211374919.8 discloses a composite solid electrolyte membrane, a preparation method thereof and a solid lithium battery, wherein the solid electrolyte membrane comprises a PVDF-HFP@PI nanofiber membrane with a core-shell structure and an electrolyte filled in pores of the solid electrolyte membrane and composed of a lithium ion conductor, a polymer and lithium salt, and the solid electrolyte membrane has excellent mechanical properties and thermal dimensional stability. Patent application document 202111591792.0 discloses a preparation method of an all-solid-state battery with a lithium supplementing sulfide solid electrolyte membrane, wherein nitrile rubber is selected as a binder for the sulfide solid electrolyte membrane, an electrostatic powder spraying device is adopted to scatter inert lithium powder on the surface of a sulfide electrolyte layer, so that the interface contact between the solid electrolyte membrane and a negative electrode pole piece can be improved while negative electrode lithium supplementing is realized, the interface impedance of the battery is reduced, and the multiplying power performance and the capacity retention rate of the battery are improved.
For example, patent application 202211739119.1 discloses a method for preparing a sulfide-polymer composite solid electrolyte membrane by molecular hybridization, and a preparation method and application thereof, wherein the molecular hybridization sulfide-polymer composite solid electrolyte membrane is obtained by reacting polyethylene glycol diacrylate with thiol-olefin of a sulfide electrolyte, and the interface compatibility problem between the organic electrolyte and the inorganic electrolyte can be greatly improved by adopting a molecular internal hybridization method, so that the internal impedance is greatly reduced. Patent application document 202211439068.0 discloses a preparation method and application of a high-concentration lithium salt sulfide composite solid electrolyte membrane, wherein a binder of the solid electrolyte membrane comprises one or more copolymers of butyl acrylate, ethyl acrylate, polyethylene glycol diacrylate and polymethyl methacrylate, and the membrane has the advantages of low porosity, higher ion conductivity, high migration number, good contact with lithium metal and the like, is simple in preparation process, does not need a large amount of organic solvents, and can be used for mass production. Patent application document 202011597001.0 discloses an electrolyte membrane for a sulfide solid state battery, and a preparation method and application thereof, wherein the sulfide solid state electrolyte membrane adopts any one or a combination of at least two of a polyethylene isolating membrane, a polypropylene isolating membrane, a polyethylene-polypropylene composite isolating membrane, a polyethylene terephthalate non-woven fabric isolating membrane and a polyimide electrospinning isolating membrane as a base membrane, and nano ceramic layers are coated on two sides of the base membrane to enable the electrolyte membrane to have high interface contact property, high strength and high ion conductivity.
However, the sulfide solid electrolyte membrane disclosed in the above related art has a high ionic conductivity or good mechanical properties, but has a problem of compatibility with a high-voltage positive electrode. Therefore, the development of sulfide solid electrolyte membranes suitable for high voltage positive electrode systems remains significant.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the insufficient sulfide electrolyte-high voltage positive electrode compatibility is related to the thermodynamic instability of the surface defect (containing a large amount of mercapto functional groups) of sulfide particles, and the inventor researches and discovers that the sulfide particles with high pressure resistance are synthesized first, and then the thermodynamic stability of the sulfide particles is further improved by carrying out functionalization treatment on the surfaces of the sulfide particles, so that the compatibility of the sulfide solid electrolyte membrane with the high voltage positive electrode is hopeful to be solved.
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, embodiments of the present invention provide a sulfide solid electrolyte membrane, a method of manufacturing the same, and an all-solid alkali metal ion battery.
The embodiment of the invention provides a sulfide solid electrolyte membrane, which consists of sulfide particles containing a polymer coating, wherein the chemical composition of the sulfide particles containing the polymer coating is [ E ] m M n S o ] C α O β S γ H δ N ζ E a The method comprises the steps of carrying out a first treatment on the surface of the Wherein [ E m M n S o ]Is sulfide particles, E is selected from Li + Or Na (or) + M is selected from Si 4+ 、Ge 4+ 、Se 4+ Or Sn (Sn) 4+ And is less than or equal to 3m≤8，1≤n≤2，2≤o≤8；C α O β S γ H δ N ζ E a Is a polymer coating layer forming a disulfide bond with the surface of the sulfide particles, andαis selected from the group consisting of 0.0001 to 1,βis selected from the group consisting of 0 to 0.5,γis selected from the group consisting of 0.000001-1,δselected from the group consisting of 0.00001-2,ζselected from 0-0.01, and a is selected from 0-0.0001.
The sulfide solid electrolyte membrane provided by the embodiment of the invention has the following advantages and technical effects:
(1) Sulfide particles [ E ] m M n S o ]The sulfide solid electrolyte membrane has high-pressure resistance, and is beneficial to improving the high-pressure resistance of the sulfide solid electrolyte membrane.
(2) In the sulfide particles containing the polymer coating, the polymer coating is connected with the surfaces of the sulfide particles through a disulfide bond (S-S bond), so that a cross-linked network structure is formed inside the whole sulfide solid electrolyte membrane, and the polymer coating forms an artificial protection layer with high oxidation stability on the surfaces of the sulfide particles, so that the thermodynamic stability of the high-voltage positive electrode is improved, and the compatibility of the sulfide solid electrolyte membrane and the high-voltage positive electrode is improved.
(3) Due to S-S bonds on the surface of sulfide particles, the electron cloud density on S can be obviously increased, so that the acting force between S and alkali metal ions is enhanced, and under a high voltage state, the strong acting force between S and alkali metal ions limits the separation of alkali metal ions from electrolyte from a kinetic angle, and limits S 2- The high voltage stability of the sulfide solid electrolyte membrane of the embodiment of the invention is improved, so that the sulfide solid electrolyte membrane has a wider electrochemical window, and the high voltage cycle performance of the all-solid alkali metal ion battery can be improved.
(4) The abundant S-S bonds have a reversible fracture-generation function at room temperature, can provide excellent self-repairing capability for the sulfide solid electrolyte membrane of the embodiment of the invention, ensure the mechanical stability of the sulfide solid electrolyte membrane structure and the close contact between the sulfide solid electrolyte membrane structure and an electrode in the battery cycle process, and improve the cycle stability and the multiplying power performance of the battery.
(5) The design of the solid sulfide electrolyte provided by the embodiment of the invention can enable the sulfide solid electrolyte membrane to have excellent ion conductivity, ensure good ion transmission performance of an electrode interface, and improve the cycle stability and the rate capability of the all-solid alkali metal ion battery.
(6) The sulfide solid electrolyte membrane of the embodiment of the invention does not generate obvious chemical/electrochemical side reaction with the high-voltage positive electrode active material, can well buffer the volume change of the positive electrode active material in the charge and discharge process, ensures that the all-solid alkali metal ion battery has good interface contact in the whole charge and discharge period, reduces the interface impedance of the battery, and improves the cycle stability and the multiplying power performance of the battery.
In some embodiments, the mass fraction of the sulfide particles is 80-99% and the mass fraction of the polymer coating is 1-20% based on 100% total mass of the sulfide solid electrolyte membrane.
In some embodiments, the sulfide solid electrolyte membrane has a thickness of 15-35 μm.
In addition, the embodiment of the invention also provides a preparation method of the sulfide solid electrolyte membrane, which comprises the following steps:
s1, mixing the sulfide particles with a binder, and performing ball milling treatment in a dry atmosphere to obtain the sulfide particles containing the polymer coating; the binder is a polymer containing terminal mercaptan and a disulfide bond structure;
s2, carrying out hot pressing treatment on the sulfide particles containing the polymer coating to obtain the sulfide solid electrolyte membrane.
The preparation method provided by the embodiment of the invention has the following advantages and technical effects:
(1) Compared with the sulfide solid electrolyte membrane in the related art, the sulfide solid electrolyte membrane provided by the inventionThe electrolyte membrane has excellent ionic conductivity (e.g., 0.5-8 mS/cm) and mechanical properties (e.g., 10-100 MPa tensile strength), a wide electrochemical window (e.g., 5.5-6.0V vs Li/Li) + ) The high-voltage all-solid-state battery has the advantages that the high-voltage all-solid-state battery does not generate obvious chemical/electrochemical side reaction with the high-voltage anode active material, and the performance of the high-voltage all-solid-state battery can be obviously improved; this advantage is related to the formation of the disulfide bonds with the surface of the sulfide particles of the binder containing the terminal mercaptan and the disulfide bond structure, as well as the high self-healing capacity of the system itself.
(2) In the preparation method of the embodiment of the invention, ball milling treatment is needed in the step (1), and the terminal mercaptan in the binder and the mercapto functional group on the surface of the sulfide particle generate a disulfide bond under the ball milling condition; if a simple mixing mode is adopted, even distribution of sulfide particles cannot be realized, and the performance of the sulfide solid electrolyte membrane is affected.
(3) In the preparation method of the embodiment of the invention, the ball milling treatment in the step (1) is performed in a dry atmosphere in order to avoid deterioration of sulfide particles.
In some embodiments, in step S1, the structural formula of the binder is formula (1):
wherein x is selected from 10 to 1000, y and z are each independently selected from 0 to 2000;
a and C are each independently selected from H, cl, CN or methyl;
b and D are each independently selected from an alkoxycarbonyl group having ten or less carbons, a cyano group, a carbamoyl group, a group having a terminal carboxylate structure having ten or less carbons, a group represented by formula (2), a group represented by formula (3), or a group represented by formula (4), wherein w in formula (2) and formula (3) is each independently selected from 0 to 100;
R is selected from the group consisting of alkyl groups having ten or less carbons including a terminal mercapto group, a terminal hydroxy group, a terminal methanesulfonyl group, a terminal cyano group, a terminal alkoxyphosphoryl group, a terminal carboxylic acid or a terminal carboxylic acid derivative group.
In some embodiments, in step S1, the mass ratio of the sulfide particles to the binder is (80-99): (1-20).
In some embodiments, in step S1, the ball milling process is performed at a speed of 2000r/min or more for a time of 1h or more.
In some embodiments, in step S1, the ball milling process is performed at a speed of 2000-10000r/min for a period of 1-24 hours.
In some embodiments, in step S2, the pressure of the autoclave is 100MPa or more.
In addition, the embodiment of the invention also provides an all-solid-state alkali metal ion battery which comprises the sulfide solid electrolyte membrane of the embodiment of the invention or the sulfide solid electrolyte membrane obtained by the preparation method of the embodiment of the invention.
The all-solid-state alkali metal ion battery provided by the embodiment of the invention has the following advantages and technical effects:
the all-solid-state alkali metal ion battery provided by the embodiment of the invention has excellent cycle stability and rate capability.
Drawings
FIG. 1 is a schematic illustration of the reaction of a binder with the surface of sulfide particles to form S-S bonds in the preparation process of the present invention;
Fig. 2 is a long cycle performance at room temperature of an all-solid-state lithium ion battery of application example 2 and application comparative example 2;
fig. 3 is a long cycle performance at room temperature of an all-solid-state lithium ion battery of application example 3 and application comparative example 3;
fig. 4 is a long cycle performance at room temperature of an all-solid-state lithium ion battery of application example 5 and application comparative example 5;
fig. 5 is a long cycle performance at room temperature of an all-solid-state lithium ion battery of application example 6 and application comparative example 6.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
A sulfide solid electrolyte membrane is composed of sulfide particles containing a polymer coating layer, the chemical composition of the sulfide particles containing the polymer coating layer is [ E ] m M n S o ] C α O β S γ H δ N ζ E a The method comprises the steps of carrying out a first treatment on the surface of the Wherein [ E m M n S o ]Is sulfide particles, E is selected from Li + Or Na (or) + M is selected from Si 4+ 、Ge 4+ 、Se 4+ Or Sn (Sn) 4+ And is less than or equal to 3m≤8，1≤n≤2，2≤o≤8；C α O β S γ H δ N ζ E a A polymer coating layer forming a disulfide covalent bond with the surface of the sulfide particles, andαis selected from the group consisting of 0.0001 to 1,βis selected from the group consisting of 0 to 0.5,γis selected from the group consisting of 0.000001-1,δselected from the group consisting of 0.00001-2, ζSelected from 0-0.01, and a is selected from 0-0.0001.
S-S bond formed between the polymer coating and the surface of the sulfide particle enables the whole sulfide solid electrolyte membrane to form a cross-linked network structure, so that the polymer coating forms an artificial protection layer with high oxidation stability on the surface of the sulfide particle, and the thermodynamic stability of the polymer coating and the high-voltage anode is improved. In addition, due to S-S bonds on the surface of sulfide particles, the electron cloud density on S can be obviously increased, so that the acting force between S and Li is enhanced, and under a high voltage state, the strong acting force between S and Li limits the Li+ from being separated from the electrolyte from the dynamic angle, and the S is limited 2- Thereby improving the high voltage stability of the sulfide solid electrolyte membrane. Meanwhile, the abundant oversulphide bonds can also enable the whole sulfide solid electrolyte membrane to have excellent self-repairing capability, so that the stress caused by the volume expansion of the electrode can be resisted, and the structural integrity of the sulfide solid electrolyte membrane can be maintained. The sulfide solid electrolyte membrane can buffer the volume change of the positive electrode active material in the charge and discharge process, so that the battery has good interface contact in the whole charge and discharge period, and the electrolyte membrane has high ionic conductivity to ensure electricity The ion transmission performance of the polar interface is good, and the cycle stability and the multiplying power performance of the battery are improved.
In some embodiments, the mass fraction of the sulfide particles is 80-99% and the mass fraction of the polymer coating is 1-20% based on 100% total mass of the sulfide solid electrolyte membrane. When the mass fraction of the sulfide particles is too low and the mass fraction of the polymer coating is too high, it is disadvantageous to improve the ion transport performance of the sulfide solid electrolyte membrane. When the mass fraction of the sulfide particles is too high and the mass fraction of the polymer coating is too low, it is disadvantageous to improve the mechanical properties of the sulfide solid electrolyte membrane.
In some embodiments, the sulfide solid electrolyte membrane has a thickness of 15-35 μm. When the film thickness is too low, the cycle performance of the all-solid-state alkali metal ion battery is disadvantageously improved, and the battery is easy to cause internal short circuit to cause battery safety accidents. When the film thickness is too thick, the rate performance of the all-solid-state alkali metal ion battery is disadvantageously improved.
In addition, the embodiment of the invention also provides a preparation method of the sulfide solid electrolyte membrane, which comprises the following steps:
s1, mixing the sulfide particles with a binder, and performing ball milling treatment in a dry atmosphere to obtain the sulfide particles containing the polymer coating; the binder is a polymer containing terminal mercaptan and a disulfide bond structure;
S2, carrying out hot pressing treatment on the sulfide particles containing the polymer coating to obtain the sulfide solid electrolyte membrane.
Sulfide particles [ E ] m M n S o ]Is a sulfide electrolyte resistant to high voltage; meanwhile, as shown in fig. 1, the binder containing the terminal mercaptan and the disulfide bond structure in the ball milling treatment in the step (1) can construct a protective layer on the surface of sulfide particles by forming an S-S bond, so that the thermodynamic stability of the high-voltage positive electrode is improved, and the compatibility of the sulfide solid electrolyte membrane and the high-voltage positive electrode is cooperatively improved. Compared with sulfide solid electrolyte membranes in the related art, the electron cloud density on S is significantly increased due to S-S bonds on the surfaces of sulfide particles, so that S is compared with alkali metalsThe acting force between ions is enhanced, and under the high voltage state, the strong acting force between S and alkali metal ions limits the separation of the alkali metal ions from the electrolyte from the dynamic angle, so that S is limited 2- Thereby improving the high voltage stability of the sulfide solid electrolyte membrane. And the S-S bond rich in the binder and the new S-S bond formed between the binder and the sulfide particles have a reversible fracture-generation function at room temperature, can provide self-repairing capability for the solid sulfide electrolyte membrane, and ensure the mechanical stability of the electrolyte membrane structure and the close contact between the electrolyte membrane structure and an electrode in the battery cycle process.
In the preparation method according to the embodiment of the present invention, the ball milling treatment in the step (1) is performed in a dry atmosphere to avoid deterioration of sulfide particles. The drying atmosphere is not particularly limited as long as it does not react with the sulfide particles, the binder, and the sulfide solid electrolyte membrane and ensures safety, and may be an inert gas such as argon or nitrogen, or may be a mixed gas of oxygen or air and an inert gas; when oxygen or air is contained in the dry atmosphere, the proportion of oxygen or air cannot be excessively high, so that explosion is avoided.
In some embodiments, in step S1, the structural formula of the binder is formula (1):
wherein x is selected from 10 to 1000, y and z are each independently selected from 0 to 2000;
a and C are each independently selected from H, cl, CN or methyl;
b and D are each independently selected from an alkoxycarbonyl group having ten or less carbons, a cyano group, a carbamoyl group, a group having a terminal carboxylate structure having ten or less carbons, a group represented by formula (2), a group represented by formula (3), or a group represented by formula (4), wherein w in formula (2) and formula (3) is each independently selected from 0 to 100;
R is selected from the group consisting of alkyl groups having ten or less carbons including a terminal mercapto group, a terminal hydroxy group, a terminal methanesulfonyl group, a terminal cyano group, a terminal alkoxyphosphoryl group, a terminal carboxylic acid or a terminal carboxylic acid derivative group.
The adhesive with the structural general formula shown in the formula (1) can more effectively improve the compatibility of the sulfide solid electrolyte membrane and the high-voltage anode and the self-repairing capability of the sulfide solid electrolyte membrane.
In some embodiments, in step S1, the mass ratio of the sulfide particles to the binder is (80-99): (1-20). When the mass ratio of the sulfide particles to the binder is too high, it is disadvantageous to improve the mechanical properties of the sulfide solid electrolyte membrane. When the mass ratio of the sulfide particles to the binder is too low, it is disadvantageous to improve the ion transport performance of the sulfide solid electrolyte membrane.
In some embodiments, in step S1, the ball milling process is performed at a speed of 2000r/min or more for a time of 1h or more. The ball milling speed and the ball milling time are met, so that uniform mixing of sulfide particles and a binder is facilitated, and further the performance of the sulfide solid electrolyte membrane is improved. Preferably, the ball milling process is performed at a speed of 2000-10000r/min, for example 2000r/min, 3000r/min, 4000r/min, 5000r/min, 6000r/min, 7000r/min, 8000r/min, 9000r/min, 10000r/min, etc., for a period of 1-24 hours, for example 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 24 hours, etc., because the improvement of the above effect is not obvious when the ball milling process is performed at an excessive speed or for an excessive time, but is disadvantageous to the cost reduction and the efficiency improvement.
In some embodiments, in step S2, the pressure of the autoclave is 100MPa or more. The above pressure conditions are satisfied, which contributes to the improvement of the ion transport performance and mechanical properties of the sulfide solid electrolyte membrane. Preferably, the pressure of the hot pressing treatment is 100-1000MPa, for example, 100MPa, 200MPa, 300MPa, 400MPa, 500MPa, 600MPa, 700MPa, 800MPa, 900MPa, 1000MPa, etc., because when the pressure of the hot pressing treatment is too large, the improvement of the above effect is not obvious, but is disadvantageous in terms of cost reduction and efficiency improvement.
In addition, the embodiment of the invention also provides an all-solid-state alkali metal ion battery which comprises the sulfide solid electrolyte membrane of the embodiment of the invention or the sulfide solid electrolyte membrane obtained by the preparation method of the embodiment of the invention.
The all-solid-state alkali metal ion battery provided by the embodiment of the invention can be an all-solid-state lithium ion battery, an all-solid-state sodium ion battery or an all-solid-state potassium ion battery, and has excellent cycle stability and rate capability.
The positive electrode of the all-solid-state alkali metal ion battery according to the embodiment of the invention is not particularly limited, and may be any positive electrode in the related art, for example, a high-voltage positive electrode or a high-specific capacity sulfur selenium compound positive electrode. For example, the positive electrode active material of the high voltage positive electrode may include lithium cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium nickel manganate, lithium cobalt manganate, lithium-rich manganese-based material, nickel manganese spinel or Na x PR(CN) 6 (P and R are each independently selected from at least one of Fe, co, ni or Mn, x is 1-2), sodium vanadium phosphate, sulfur, sodium iron sulfate, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, sodium manganese oxide, sodium cobalt oxide, and the like. The positive electrode active material of the high specific capacity sulfur-selenium compound positive electrode can comprise elemental sulfur, elemental selenium, titanium disulfide, molybdenum disulfide and LiTi 2 (PS 4 ) 3 、LiTi 2 (P(S x Se y ) 4 ) 3 (x+y = 1)、NaTi 2 (PS 4 ) 3 And NaTi 2 (P(S x Se y ) 4 ) 3 (x+y=1), and the like.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 8 GeS 6 ] 3 C 0.000221 O 0.000086 S 0.00015 7 H 0.000031 Wherein, [ Li ] 8 GeS 6 ]As sulphide particles, C 0.000221 O 0.000086 S 0.000157 H 0.000031 A polymer coating that forms a disulfide covalent bond with the surface of the sulfide particles.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under the condition of dry argon, sulfide particles [ Li ] 8 GeS 6 ]Adhesive A1 containing terminal mercaptan and persulfate bond structureThe method comprises the steps of carrying out a first treatment on the surface of the x=1000, y=100) was mixed and ball-milled at a mass ratio of 99% to 1%, a ball-milling speed of 2000 r/min and a ball-milling time of 1 h, to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 8 GeS 6 ] 3 C 0.000221 O 0.000086 S 0.000157 H 0.000031 From sulphide particles [ Li 8 GeS 6 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.000221 O 0.000086 S 0.000157 H 0.000031 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 100 MPa to obtain a sulfide solid electrolyte membrane with the thickness of 15 mu m.
Application example 1
An all-solid lithium ion battery is a lithium nickel manganese oxide/Li all-solid battery assembled based on the sulfide solid electrolyte membrane of example 1.
Example 2
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 4 SiS 4 ] 38 C 0.0122 S 0.0003 H 0.0010 N 0.0047 Wherein, [ Li ] 4 SiS 4 ]As sulphide particles, C 0.0122 S 0.0003 H 0.0010 N 0.0047 Covalent bonding to sulfide particle surfacesPolymer coating of bonds.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under the condition of dry argon, sulfide particles [ Li ] 4 SiS 4 ]Adhesive A2 containing terminal mercaptan and persulfate bond structureThe method comprises the steps of carrying out a first treatment on the surface of the x=10, y=1000) is mixed and ball-milled according to the mass ratio of 87.5 percent to 12.5 percent, the ball-milling speed is 2000 r/min, and the ball-milling time is 20 h, thus obtaining sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 4 SiS 4 ] 38 C 0.0122 S 0.0003 H 0.0010 N 0.0047 From sulphide particles [ Li 4 SiS 4 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.0122 S 0.0003 H 0.0010 N 0.0047 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 400 MPa to obtain a sulfide solid electrolyte membrane with the thickness of 20 mu m.
Application example 2
An all-solid lithium ion battery is LiNi assembled based on sulfide solid electrolyte membrane of example 2 0.8 Co 0.1 Mn 0.1 O 2 Li all-solid state battery.
Example 3
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 8 SeS 6 ] 24.5 C 0.0075 O 0.0027 S 0.0027 H 0.000 6 N 0.0010 Wherein, [ Li ] 8 SeS 6 ]As sulphide particles, C 0.0075 O 0.0027 S 0.0027 H 0.0006 N 0.0010 For forming a polysulfide covalent bond with the surface of sulfide particlesAnd (3) coating a compound.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, sulfide particles [ Li ] are subjected to dry argon atmosphere 8 SeS 6 ]Adhesive A3 containing terminal mercaptan and persulfate bond structureThe method comprises the steps of carrying out a first treatment on the surface of the x=100; y=100; z=100) was mixed and ball-milled at a mass ratio of 94.1%:5.9% at a ball milling speed of 2000 r/min for a ball milling time of 1 h to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 8 SeS 6 ] 24.5 C 0.0075 O 0.0027 S 0.0027 H 0.0006 N 0.0010 From sulphide particles [ Li 8 SeS 6 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.0075 O 0.0027 S 0.0027 H 0.0006 N 0.0010 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 1000 MPa to obtain the sulfide solid electrolyte membrane with the thickness of 22 mu m.
Application example 3
An all-solid lithium ion battery is LiCoO assembled based on sulfide solid electrolyte membrane of example 3 2 Li all-solid state battery.
Example 4
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 7 SnS 5.5 ] 25.6 C 0.0017 O 0.0009 S 0.00063 H 0.000 29 Wherein, [ Li ] 7 SnS 5.5 ]As sulphide particles, C 0.0017 O 0.0009 S 0.00063 H 0.00029 A polymer coating that forms a disulfide covalent bond with the surface of the sulfide particles.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under the condition of dry argon, sulfide particles [ Li ] 7 SnS 5.5 ]Polymer binder A4 containing terminal mercaptan and persulfate linkage structureThe method comprises the steps of carrying out a first treatment on the surface of the x=200, y=100, z=1000) was mixed and ball-milled at a mass ratio of 95.5% to 4.5% at a ball-milling speed of 2000 r/min for a ball-milling time of 18 h to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 7 SnS 5.5 ] 25.6 C 0.0017 O 0.0009 S 0.00063 H 0.00029 From sulphide particles [ Li 7 SnS 5.5 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.0017 O 0.0009 S 0.00063 H 0.00029 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 600 MPa to obtain the sulfide solid electrolyte membrane with the thickness of 28 mu m.
Application example 4
An all-solid lithium ion battery is LiCoO assembled based on sulfide solid electrolyte membrane of example 4 2 A nano-Si all-solid-state battery.
Example 5
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 3.4 Si 1.1 S 5.5 ] 71 C 0.016 O 0.0104 S 0.00011 H 0.00 2 N 2.5*10 -6 Wherein, [ Li ] 3.4 Si 1.1 S 5.5 ]As sulphide particles, C 0.016 O 0.0104 S 0.00011 H 0.002 N 2.5*10 -6 To be in contact with sulfide particlesA polymer coating that faces a disulfide covalent bond.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under the condition of dry argon, sulfide particles [ Li ] 3.4 Si 1.1 S 5.5 ]Adhesive A5 containing terminal mercaptan and persulfate bond structureThe method comprises the steps of carrying out a first treatment on the surface of the x=10, y=1000, z=500) was mixed and ball-milled at a mass ratio of 80% to 20% at a ball-milling speed of 2000 r/min for a ball-milling time of 15 h to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 3.4 Si 1.1 S 5.5 ] 71 C 0.016 O 0.0104 S 0.00011 H 0.002 N 2.5*10 -6 From sulphide particles [ Li 3.4 Si 1.1 S 5.5 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.016 O 0.0104 S 0.00011 H 0.002 N 2.5*10 -6 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 500 MPa to obtain a sulfide solid electrolyte membrane with the thickness of 31 mu m.
Application example 5
An all-solid lithium ion battery is LiNi assembled based on sulfide solid electrolyte membrane of example 5 0.8 Co 0.1 Mn 0.1 O 2 A nano-Si all-solid-state battery.
Example 6
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 7.6 SnS 5.8 ] 26 C 0.00064 O 0.00019 S 0.0003 8 H 0.000089 N 8.3*10 -7 Li 0.000039 Wherein, [ Li ] 7.6 SnS 5.8 ]As sulphide particles, C 0.00064 O 0.00019 S 0.00038 H 0.00008 9 N 8.3*10 -7 Li 0.000039 A polymer coating that forms a disulfide covalent bond with the surface of the sulfide particles.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under the condition of dry argon, sulfide particles [ Li ] 7.6 SnS 5.8 ]Polymer binder A6 containing terminal mercaptan and persulfate linkageThe method comprises the steps of carrying out a first treatment on the surface of the x=1000; y=10; z=10) was mixed and ball-milled at a mass ratio of 96.8%:3.2%, a ball milling speed of 2000 r/min, and a ball milling time of 10 h, to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Li ] 7.6 SnS 5.8 ] 26 C 0.00064 O 0.00019 S 0.00038 H 0.000089 N 8.3*10 -7 Li 0.000039 From sulphide particles [ Li 7.6 SnS 5.8 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.00064 O 0.00019 S 0.00038 H 0.00008 9 N 8.3*10 -7 Li 0.000039 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 300 MPa to obtain a sulfide solid electrolyte membrane with the thickness of 18 mu m.
Application example 6
An all-solid lithium ion battery is LiCoO assembled based on sulfide solid electrolyte membrane of example 6 2 and/mum-Si all-solid-state battery.
Example 7
An integrated sulfide solid electrolyte membrane based on a persulfate bond is composed of sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Na ] 7.6 SnS 5.8 ] 26 C 0.00064 O 0.00019 S 0.0003 8 H 0.000089 N 8.3*10 -7 Na 0.000039 Wherein, [ Na ] 7.6 SnS 5.8 ]As sulphide particles, C 0.00064 O 0.00019 S 0.00038 H 0.00008 9 N 8.3*10 -7 Na 0.000039 A polymer coating that forms a disulfide covalent bond with the surface of the sulfide particles.
The preparation method of the sulfide solid electrolyte membrane comprises the following specific operations:
s1, under dry argon, sulfide particles [ Na 7.6 SnS 5.8 ]Polymer binder A7 containing terminal mercaptan and persulfate linkage structureThe method comprises the steps of carrying out a first treatment on the surface of the x=1000, y=10, z=10) was mixed and ball-milled at a mass ratio of 96.8% to 3.2% at a ball-milling speed of 2000 r/min for a ball-milling time of 24 h to obtain sulfide solid electrolyte powder.
The sulfide solid electrolyte powder is sulfide particles containing a polymer coating, and the chemical composition of the sulfide particles containing the polymer coating is [ Na ] 7.6 SnS 5.8 ] 26 C 0.00064 O 0.00019 S 0.00038 H 0.000089 N 8.3*10 -7 Na 0.000039 From sulphide particles [ Na 7.6 SnS 5.8 ]And a polymer coating layer C coated on the surface of the sulfide particles 0.00064 O 0.00019 S 0.00038 H 0.00008 9 N 8.3*10 -7 Na 0.000039 Composition is prepared.
S2, hot-pressing the sulfide solid electrolyte powder obtained in the step S1 under 300 MPa to obtain a sulfide solid electrolyte membrane with the thickness of 18 mu m.
Application example 7
All-solid sodium ion battery, naCoO assembled based on sulfide solid electrolyte membrane of example 7 2 and/mum-Si all-solid-state battery.
Comparative example 1
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 1, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 1 was used
The all-solid lithium ion battery and the method for producing the same of the application comparative example are the same as those of example 1, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 1.
Comparative example 2
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 2, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 2 was used
The all-solid lithium ion battery and the method for preparing the same of the application comparative example are the same as those of example 2, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 2.
Comparative example 3
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 3, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 3 was used
The all-solid lithium ion battery and the method for producing the same of the application comparative example are the same as those of example 3, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 3.
Comparative example 4
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 4, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 4 was used
The all-solid lithium ion battery and the method for producing the same of the application comparative example are the same as those of example 4, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 4.
Comparative example 5
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 5, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 5 was used
The all-solid lithium ion battery and the method for producing the same of the application comparative example are the same as those of example 5, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 5.
Comparative example 6
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 6, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 6 was used
The all-solid lithium ion battery and the method for producing the same of the application comparative example are the same as those of example 6, except that the solid electrolyte membrane used is the sulfide solid electrolyte membrane of comparative example 6.
Comparative example 7
The sulfide solid electrolyte membrane of this comparative example was produced in the same manner as in example 7, except that Polytetrafluoroethylene (PTFE) was used as the binder.
Comparative example 7 was used
The all-solid sodium-ion battery of the comparative example and the method for producing the same were the same as those of example 7, except that the solid electrolyte membrane used was the sulfide solid electrolyte membrane of comparative example 7.
Performance test I: the solid sulfide electrolyte membranes of examples 1 to 7 and the solid sulfide electrolyte membranes of comparative examples 1 to 7 were tested for physicochemical properties, and the results are shown in table 1.
(1) Thickness: the sulfide solid electrolyte membranes of examples 1-7 and the sulfide solid electrolyte membranes of comparative examples 1-7 were placed on a thickness gauge and clamped, and after the readings were stabilized, the thickness of the membranes was accurately measured, and the thickness of 5 different areas was repeatedly measured for each group of samples to calculate an average value.
(2) Room temperature ionic electricityConductivity: measurement of Electrochemical Impedance Spectra (EIS) of sulfide solid electrolyte membranes of examples 1 to 7 and sulfide solid electrolyte membranes of comparative examples 1 to 7 using a multichannel electrochemical workstation (VMP-300), assembling sulfide solid electrolyte membrane steel to steel symmetrical cell, testing ac impedance spectrum at a frequency range of 100mHz to 7mHz with 10mV perturbation, reading corresponding impedance values, and calculating room temperature ion conductivity according to the formula σ=l/RS, where L is the thickness of sulfide solid electrolyte membrane in cm, R is the impedance of sulfide solid electrolyte membrane in Ω, S is the area of sulfide solid electrolyte membrane in cm 2 。
(3) Oxidative decomposition voltage: the sulfide solid state electrolyte membranes of examples 1 to 7 and the sulfide solid state electrolyte membranes of comparative examples 1 to 7 were subjected to a Linear Sweep Voltammetry (LSV) test by a multi-channel electrochemical workstation (VMP-300), and the voltage values at which the sulfide solid state electrolyte membranes of examples 1 to 7 and the sulfide solid state electrolyte membranes of comparative examples 1 to 7 began oxidative decomposition were determined by analyzing the current-voltage curve by measuring the relationship between current and voltage in the voltage range of 0 to 6.0V at a sweep rate of 1 mV/s.
(4) Tensile strength: the sulfide solid electrolyte membranes of examples 1 to 7 and the sulfide solid electrolyte membranes of comparative examples 1 to 7 were made into uniform films having a length of 70 mm and a width of 10 mm and a thickness of 0.1 mm, the prepared films were put on a jig of a universal tester (MTS E43.104), and tensile force was applied to both ends of the test sample by a universal tensile machine to obtain a change curve of stress strain, thereby obtaining tensile strength and elongation at break, and tensile properties of the sulfide solid electrolyte membranes were evaluated.
TABLE 1 chemical composition and physicochemical Properties of solid sulfide electrolyte films of examples 1 to 7
TABLE 2 chemical composition and physicochemical Properties of solid sulfide electrolyte films of comparative examples 1 to 7
From the comparison of examples 1 and comparative examples 1, 2 and 2, examples 3 and 3, examples 4 and 4, examples 5 and 5, examples 6 and 6, examples 7 and 7 in tables 1 and 2, the solid sulfide electrolyte membranes of examples 1 to 7 were significantly higher in room temperature ion conductivity, oxidative decomposition voltage, tensile strength than the solid sulfide electrolyte membranes of comparative examples 1 to 7.
Performance test II: the following tests were conducted on the capacity retention ratios of all solid-state batteries of application examples 1 to 7 and all solid-state batteries of comparative examples 1 to 7, and the results are as follows.
Application example 1 and application comparative example 1 comparison: according to 0.1C multiplying power, 2.7-5.1V (vs. Li) + Charge and discharge tests were carried out in the voltage range, the capacity retention rate of 800 cycles of the lithium nickel manganese oxide/Li all solid state lithium ion battery of application example 1 was 90%, while the capacity retention rate of the all solid state lithium ion battery of application comparative example 1 was only 30%. The mechanism of improvement of the battery cycle performance by application example 1 is: in the sulfide solid electrolyte membrane of comparative example 1 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 1 is poor in high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery to which comparative example 1 is applied. In example 1, however, the electron cloud density on S is significantly increased due to the S-S bond on the surface of the sulfide particles, so that the force between S and Li is enhanced, and the high force between S and Li under high voltage conditions limits Li from the kinetic point of view + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid electrolyte membrane and significantly improving the capacity retention rate of the all-solid lithium ion battery of application example 1.
Application example 2 and application comparative example 2 comparison: as shown in FIG. 2, the composition was prepared at a rate of 0.2C, 2.7-5.1V (vs. Li + Charging and discharging test was performed in the range of Li) voltage, liNi of example 2 was applied 0.8 Co 0.1 Mn 0.1 O 2 The capacity retention of the Li all-solid lithium ion battery was 98% for 100 cycles, whereas the capacity retention of the all-solid lithium ion battery employing comparative example 2 was only 80%. The mechanism of improvement of the battery cycle performance by application example 2 is: in the sulfide solid electrolyte membrane of comparative example 2 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 2 has poor high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 2. In example 2, however, the electron cloud density on S is significantly increased due to the S-S bond on the surface of the sulfide particles, so that the force between S and Li is enhanced, and the high force between S and Li under high voltage conditions limits Li from the kinetic point of view + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and significantly improving the capacity retention rate of the all-solid-state lithium ion battery of application example 2.
Application example 3 and comparison with application comparative example 3: as shown in FIG. 3, the composition was prepared at a rate of 0.5C, 2.7-5.1V (vs. Li + Charge and discharge test was performed in a voltage range using LiCoO of application example 3 2 The capacity retention of the Li all-solid lithium ion battery was 99% for 100 cycles, whereas the capacity retention of the all-solid lithium ion battery employing comparative example 3 was only 74%. The mechanism of improvement of the battery cycle performance by application example 3 is: in the sulfide solid electrolyte membrane of comparative example 3 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 3 has poor high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 3. In example 3, however, the electron cloud density on S is significantly increased due to S-S bonds on the surface of sulfide particles, as compared with the solid electrolyte membrane of comparative example 3 in which PTFE is used as a binderAdding, the acting force between S and Li is enhanced, and under the high voltage state, the strong acting force between S and Li limits Li from the dynamic angle + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and significantly improving the capacity retention rate of the all-solid-state lithium ion battery of application example 3.
Comparison of application example 4 and application comparative example 4: according to 0.1C multiplying power, 2.7-5.1V (vs. Li) + Charge and discharge test was performed in a voltage range using LiCoO of application example 4 2 The capacity retention of the per nano-Si all solid state lithium ion battery was 96% for 300 cycles, whereas the capacity retention of the all solid state lithium ion battery employing comparative example 4 was only 51%. The mechanism of improvement of the battery cycle performance by application example 4 is: in the sulfide solid electrolyte membrane of comparative example 4 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 4 has poor high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 4. In example 4, however, the electron cloud density on S is significantly increased due to the S-S bond on the surface of the sulfide particles, so that the force between S and Li is enhanced, and the high force between S and Li under high voltage conditions limits Li from the kinetic point of view + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and significantly improving the capacity retention rate of the all solid state lithium ion battery of application example 4.
Comparison of application example 5 and application comparative example 5: as shown in FIG. 4, the ratio of the ratio is 2.7-5.1V (vs. Li) + Charging and discharging test was performed in the range of Li) voltage, liNi of application example 5 was used 0.8 Co 0.1 Mn 0.1 O 2 The capacity retention rate of the per nano-Si all-solid state battery cycle was 97% for 100 cycles, whereas the capacity retention rate of the all-solid state lithium ion battery using comparative example 5 was only 65%. The mechanism of improvement of the battery cycle performance by application example 5 is:in the sulfide solid electrolyte membrane of comparative example 5 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 5 has poor high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 5. In example 5, however, the electron cloud density on S is significantly increased due to the S-S bond on the surface of the sulfide particles, so that the force between S and Li is enhanced, and the high force between S and Li under high voltage conditions limits Li from the kinetic point of view + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and significantly improving the capacity retention rate of the all solid state lithium ion battery of application example 5.
Comparison of application example 6 and application comparative example 6: as shown in FIG. 5, the composition was prepared at a rate of 0.1C, 2.7-5.1V (vs. Li + Charge and discharge test was performed in a voltage range using LiCoO of application example 6 2 The capacity retention of the/mum-Si all-solid lithium ion battery for 100 cycles was 94%, while the capacity retention of the all-solid lithium ion battery using comparative example 6 was only 75%. The mechanism of improvement of the battery cycle performance by application example 6 is: in the sulfide solid electrolyte membrane of comparative example 6 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 6 is poor in high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 6. In example 6, however, the electron cloud density on S is significantly increased due to S-S bonds on the surface of sulfide particles, so that the force between S and Li is enhanced, and the high force between S and Li limits Li from the kinetic point of view in a high voltage state, as compared with the sulfide solid electrolyte membrane of comparative example 6 using PTFE as a binder + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and remarkably improving the capacity retention rate of the all solid state lithium ion battery of application example 6 。
Comparison of application example 7 and application comparative example 7: according to the multiplying power of 0.1C and the multiplying power of 2.0-4.1V (vs. Na/Na) + ) Charge and discharge tests were carried out in the voltage range using NaCoO of application example 7 2 The capacity retention of the/mum-Si all-solid-state battery for 50 cycles was 90%, while the capacity retention of the all-solid-state sodium ion battery using comparative example 7 was only 70%. The mechanism of improvement of the battery cycle performance by application example 7 is: in the sulfide solid electrolyte membrane of comparative example 7 using PTFE as a binder, only physical coating is performed between PTFE and sulfide solid particles, and covalent bonds are not formed, so that the sulfide solid electrolyte membrane of comparative example 7 has poor high-voltage stability, resulting in a low capacity retention rate of the all-solid lithium ion battery using comparative example 7. In example 7, however, the electron cloud density on S is significantly increased due to the S-S bond on the surface of the sulfide particles, so that the force between S and Na is enhanced, and the strong force between S and Li under high voltage state limits Na from the kinetic point of view + Is separated from the electrolyte, limits S 2- Thereby improving the high voltage stability of the sulfide solid state electrolyte and significantly improving the capacity retention rate of the all solid state lithium ion battery of application example 7.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A sulfide solid electrolyte membrane comprising sulfide particles having a polymer coating layer, wherein the sulfide particles having a chemical composition of [ E ] m M n S o ] C α O β S γ H δ N ζ E a The method comprises the steps of carrying out a first treatment on the surface of the Wherein [ E m M n S o ]Is sulfide particles, E is selected from Li + Or Na (or) + M is selected from Si 4+ 、Ge 4+ 、Se 4+ Or Sn (Sn) 4+ And is less than or equal to 3m≤8，1≤n≤2，2≤o≤8；C α O β S γ H δ N ζ E a Is a polymer coating layer forming a disulfide bond with the surface of the sulfide particles, andαis selected from the group consisting of 0.0001 to 1,βis selected from the group consisting of 0 to 0.5,γis selected from the group consisting of 0.000001-1,δselected from the group consisting of 0.00001-2,ζselected from 0-0.01, and a is selected from 0-0.0001.
2. The sulfide solid electrolyte membrane according to claim 1, wherein the mass fraction of the sulfide particles is 80 to 99% and the mass fraction of the polymer coating layer is 1 to 20% based on 100% of the total mass of the sulfide solid electrolyte membrane.
3. Sulfide solid electrolyte membrane according to claim 1 or 2, characterized in that the thickness of the sulfide solid electrolyte membrane is 15-35 μm.
4. A method for producing a sulfide solid electrolyte membrane according to any one of claims 1 to 3, characterized by comprising the steps of:
s1, mixing the sulfide particles with a binder, and performing ball milling treatment in a dry atmosphere to obtain the sulfide particles containing the polymer coating; the binder is a polymer containing terminal mercaptan and a disulfide bond structure;
s2, carrying out hot pressing treatment on the sulfide particles containing the polymer coating to obtain the sulfide solid electrolyte membrane.
5. The method for producing a sulfide solid electrolyte membrane according to claim 4, wherein in step S1, the structural general formula of the binder is formula (1):
wherein x is selected from 10 to 1000, y and z are each independently selected from 0 to 2000;
a and C are each independently selected from H, cl, CN or methyl;
b and D are each independently selected from an alkoxycarbonyl group having ten or less carbons, a cyano group, a carbamoyl group, a group having a terminal carboxylate structure having ten or less carbons, a group represented by formula (2), a group represented by formula (3), or a group represented by formula (4), wherein w in formula (2) and formula (3) is each independently selected from 0 to 100;
r is selected from the group consisting of alkyl groups having ten or less carbons including a terminal mercapto group, a terminal hydroxy group, a terminal methanesulfonyl group, a terminal cyano group, a terminal alkoxyphosphoryl group, a terminal carboxylic acid or a terminal carboxylic acid derivative group.
6. The method for producing a sulfide solid electrolyte membrane according to claim 4, characterized in that in step S1, a mass ratio of the sulfide particles and the binder is (80-99): (1-20).
7. The method for producing a sulfide solid electrolyte membrane according to claim 4, wherein in step S1, the ball milling treatment is performed at a speed of 2000r/min or more for a time of 1 h or more.
8. The method for producing a sulfide solid electrolyte membrane according to claim 7, wherein in step S1, the ball milling treatment is performed at a speed of 2000 to 10000r/min for a time of 1 to 24 hours.
9. The method for producing a sulfide solid electrolyte membrane according to claim 4, wherein in step S2, the pressure of the heat pressing treatment is 100MPa or more.
10. An all-solid alkali metal ion battery comprising the sulfide solid electrolyte membrane according to any one of claims 1 to 3, or the sulfide solid electrolyte membrane obtained by the production method according to any one of claims 4 to 9.
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