CN116864624A - Electrode plate of integrated sulfide all-solid-state battery and preparation method thereof - Google Patents
Electrode plate of integrated sulfide all-solid-state battery and preparation method thereof Download PDFInfo
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- CN116864624A CN116864624A CN202310780510.4A CN202310780510A CN116864624A CN 116864624 A CN116864624 A CN 116864624A CN 202310780510 A CN202310780510 A CN 202310780510A CN 116864624 A CN116864624 A CN 116864624A
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000011267 electrode slurry Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- ISJNWFZGNBZPQE-UHFFFAOYSA-N germanium;sulfanylidenesilver Chemical compound [Ge].[Ag]=S ISJNWFZGNBZPQE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 15
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 18
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 229920002367 Polyisobutene Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920001249 ethyl cellulose Polymers 0.000 claims description 9
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000002003 electrode paste Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229920006311 Urethane elastomer Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 7
- 238000003892 spreading Methods 0.000 abstract description 4
- 230000007480 spreading Effects 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 8
- 229920003225 polyurethane elastomer Polymers 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- 229910021617 Indium monochloride Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- 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
- H01M10/42—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- H01M2300/008—Halides
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
Abstract
The invention discloses a preparation method of an integrated sulfide all-solid-state battery electrode slice, which comprises the steps of mixing a binder with a solvent, adding a conductive agent, lithium nickel manganese oxide and a sulfur silver germanium ore solid electrolyte, stirring to obtain electrode slurry, spreading the electrode slurry on an aluminum foil, and drying to obtain an anode electrode slice; and then mixing the binder, the solvent and the sulfur silver germanium ore solid electrolyte, coating the mixture on the prepared positive electrode plate, drying the mixture, and carrying out multilayer coating. The preparation method of the electrode plate of the all-solid-state battery of the integrated sulfide solves the problem of solid-solid interface contact of the solid battery. The electrode plate manufacturing method provided by the invention has the advantages of low toxicity, good fluidity, low cost, thermodynamic stability to sulfide electrolyte and the like, and is suitable for preparing sulfide all-solid-state soft-package batteries.
Description
Technical Field
The invention relates to the field of sulfide all-solid-state batteries, in particular to an integrated sulfide all-solid-state battery electrode plate and a preparation method thereof as well as a preparation method of a soft package battery.
Background
All-solid-state lithium batteries are considered to be the most promising new generation energy storage devices as next generation power batteries and energy storage power stations due to their high volumetric energy density, as well as intrinsic safety. All-solid batteries can be classified into sulfides, polymers, oxides, halides, and the like depending on the kind of all-solid electrolyte. Among them, sulfide electrolyte has the highest lithium ion conductivity and better mechanical property, and is favored by the academia and industry. The halide electrolyte is believed to be interface-friendly to the oxide anode and is suitable for use as a protective layer between the oxide anode and the sulfide electrolyte to isolate interfacial side reactions. The present invention therefore focuses primarily on the use of sulfide electrolytes as the ion-conducting host and the use of halide electrolytes as the protective layer.
The currently mainstream sulfide all-solid-state lithium batteries can be divided into: (1) Cold-pressed dry powder type die batteries for laboratory mechanism studies, (2) soft-pack laminated pouch type batteries for mass production. The former can well realize the work of the all-solid-state battery because the quantity of the positive electrode active material is small and the fixed rigid mould is used for giving pressure support. However, the latter is not commercialized because of the problems of the current large-scale pole piece preparation process, solid-solid interface contact and the like, and the realization of the soft package lamination type all-solid-state battery with large capacity is not yet achieved.
At present, the electrode plate mainly comprises a binder, a conductive agent, an active substance and the like, and the components are dispersed and coated on a corresponding current collector through a solvent to obtain the final electrode plate. The solvent and the binder are used as the supporting materials of the electrode plate, and the electrode plate needs to have the advantages of chemical/electrochemical stability with active substances, good mechanical strength, low cost, low toxicity, simple processing and the like. The main solvents and binders of conventional organic liquid batteries are N-methylpyrrolidone (NMP) and polyvinylidene fluoride (PVDF), respectively. However, NMP is a highly polar solvent, which is prone to nucleophilic reactions in sulfide electrolytes, and thus damages the structure of sulfide electrolytes. And the selection of binders also requires low polarity according to similar principles of miscibility, which makes it difficult to directly transition from the electrode sheet preparation process of a liquid battery to an all-solid-state sulfide battery.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to solve the following problems with the existing sulfide all-solid-state battery electrode sheet: (1) Solving the thermodynamic stability between the sulfide electrolyte/oxide anode and the composite cathode; (2) The solid-solid state sulfide battery without a physical interface is built, so that the solid-solid fixation problem of the solid state battery is greatly reduced; (3) the existing all-solid-state battery cannot be folded; (4) The existing all-solid-state sulfide battery can not realize high-speed charging and discharging.
In order to achieve the above object, the present invention provides an integrated sulfide all-solid-state battery electrode sheet, comprising an anode portion: the lithium nickel manganese oxide electrolyte comprises a binder, a solvent, a conductive agent, a sulfur silver germanium ore solid electrolyte and lithium nickel manganese oxide, wherein the mass ratio of the binder to the solvent to the conductive agent to the sulfur silver germanium ore solid electrolyte to the lithium nickel manganese oxide is 1:5:1:3:7.
Further, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
Further, the solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
Further, the conductive agent includes one or more of Super P, VGCF, acetylene black, ketjen black.
Further, the chemical formula of the lithium nickel manganese oxide is LiNi 0.9 Co 0.05 Mn 0.05 O 2 。
Further, the chemical formula of the sulfur silver germanium ore solid electrolyte is Li 6 PS 5 Cl。
The invention further provides a preparation method of the integrated sulfide all-solid-state battery electrode slice, which comprises the steps of mixing a binder with a solvent, adding a conductive agent, lithium nickel manganese oxide and a sulfur silver germanium ore solid electrolyte, stirring to obtain electrode slurry, spreading the electrode slurry on an aluminum foil, and drying to obtain the positive electrode slice.
Further, the stirring time of the polar paste is 1h-10h.
Further, the drying temperature of the electrode slurry is 60-180 ℃.
Further, the binder, the solvent and the halide solid electrolyte are mixed, stirred and coated on the prepared positive electrode plate to serve as a positive sulfide interface protective layer, and dried, wherein the mass ratio of the components is 1:12:4.
Further, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
Further, the solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
Further, the halide electrolyte has the chemical formula of Li 3 InCl 6
Further, the stirring time of the electrode paste is 1h to 10h.
Further, the drying temperature of the electrode slurry is 60-180 ℃.
Further, the binder, the solvent and the sulfide solid electrolyte are then mixed, stirred and coated on the pole piece in the previous step, and dried, wherein the mass ratio of the components is 1:28:8.
Further, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
Further, the solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
Further, the chemical formula of the sulfur silver germanium ore solid electrolyte is Li 6 PS 5 Cl。
Further, the stirring time of the polar paste is 1h-10h.
Further, the drying temperature of the electrode slurry is 60-180 ℃.
Further, the binder, the solvent, the silicon powder and the hard carbon are mixed and stirred and coated on the pole piece in the previous step, and are dried, wherein the mass ratio of the components is 1:28:8:8.
Further, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
Further, the solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
Further, the stirring time of the electrode paste is 1h to 10h.
Further, the drying temperature of the electrode slurry is 60-180 ℃.
And finally, applying the copper-lithium composite belt on the pole piece in the last step, packaging, welding the pole lug, and thus completing the preparation of the soft-package solid-state battery.
Technical effects
The electrode plate (comprising the anode, the anode protection layer, the electrolyte layer and the cathode layer) of the integrated sulfide all-solid-state battery has the advantages of softness, easiness in processing, low cost, integrated anode-cathode interface, excellent electrochemical cycle performance and capability of realizing high-rate high-speed charge and discharge. The method provided by the embodiment of the invention is used for packaging the multi-layer coated pole piece to obtain the all-solid-state soft-packaged battery, and the interface contact impedance of the solid-state battery is relieved due to the integrated structure, so that the excellent electrochemical performance of which the capacity retention rate is over 99% in 100 circles is realized under the multiplying power of 3C after the all-solid-state soft-packaged battery is assembled.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 is a schematic diagram of bending and tiling an electrode plate of an integrated sulfide all-solid-state battery and a physical diagram of a soft-package battery;
fig. 2 is a charge-discharge cycle diagram of a sulfide soft pack all-solid-state lithium battery according to a preferred embodiment of the present invention at a charge-discharge rate of 0.1C;
fig. 3 is a charge-discharge cycle diagram of a sulfide soft pack all-solid-state lithium battery according to a preferred embodiment of the present invention at a charge-discharge rate of 3C.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular internal procedures, techniques, etc. in order to provide a thorough understanding of embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
The invention provides a sulfide all-solid-state battery electrode positive plate which comprises a binder, a solvent, a conductive agent, a sulfur silver germanium ore solid electrolyte and lithium nickel manganese oxide, wherein the mass ratio of the binder to the solvent to the conductive agent to the sulfur silver germanium ore solid electrolyte to the lithium nickel manganese oxide is 1:5:1:3:7. In an embodiment of the present invention, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate, and ethyl cellulose.
The solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
The conductive agent comprises one or more of Super P, VGCF, acetylene black and ketjen black.
The chemical formula of the lithium nickel manganese oxide is LiNi 0.6 Co 0.2 Mn 0.2 O 2 。
The chemical formula of the sulfur silver germanium ore solid electrolyte is Li 6 PS 5 Cl。
The stirring time of the electrode slurry is 1h-10h.
The drying temperature of the electrode slurry is 60-180 ℃.
The drying temperature of the multilayer coating is 100-130 ℃.
The invention further provides a preparation method of the electrode plate of the integrated sulfide all-solid-state battery, which comprises the steps of mixing a binder with a solvent, adding a conductive agent, lithium nickel manganese oxide and a sulfur silver germanium ore solid electrolyte, stirring to obtain electrode slurry, spreading the electrode slurry on an aluminum foil, and drying to obtain an anode electrode plate; then mixing and stirring a binder, a solvent and a sulfur silver germanium ore halide solid electrolyte, coating the mixture on a prepared positive electrode plate to serve as a positive sulfide interface protective layer, and drying, wherein the mass ratio of the components is 1:12:4; then, mixing and stirring a binder, a solvent and a sulfide solid electrolyte, coating the mixture on the pole piece in the previous step, and drying the pole piece, wherein the mass ratio of the components is 1:28:8; then, the binder, the solvent, the silicon powder and the hard carbon are mixed, stirred and coated on the pole piece in the previous step, and dried, wherein the mass ratio of the components is 1:28:8:8. Realizing the multilayer coating of the electrode plate.
Mixing a binder with a solvent, adding a conductive agent, lithium nickel manganese oxide and a sulfur silver germanium ore solid electrolyte, stirring to obtain electrode slurry, and spreading the electrode slurry on an aluminum foil and drying to obtain a positive electrode plate, wherein the stirring time of the electrode slurry is 1-10 h. The drying temperature of the electrode slurry is 60-180 ℃. The drying temperature of the multilayer coating is 100-130 ℃.
Further, the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
The solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
The halide electrolyte has the chemical formula of Li 3 InCl 6
The stirring time of the electrode slurry is 1h-10h.
The drying temperature of the electrode slurry is 60-180 ℃.
Then, mixing and stirring the binder, the solvent and the sulfide solid electrolyte, coating the mixture on the pole piece in the previous step, and drying, wherein the mass ratio of the components is 1:28:8, and the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
The solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
The chemical formula of the sulfur silver germanium ore solid electrolyte is Li 6 PS 5 Cl。
The stirring time of the electrode slurry is 1h-10h.
The drying temperature of the electrode slurry is 60-180 ℃.
Then, mixing and stirring the binder, the solvent, the silicon powder and the hard carbon, coating the mixture on the pole piece in the previous step, and drying the pole piece, wherein the mass ratio of the components is 1:28:8:8. In the course of this process, the process,
the binder comprises one or more of epoxy resin, polyurethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate and ethyl cellulose.
The solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane and n-heptane.
The stirring time of the electrode slurry is 1h-10h.
The drying temperature of the electrode slurry is 60-180 ℃.
The sulfide all-solid-state battery electrode positive plate with the multilayer coating is finished, a copper-lithium composite belt is stuck on the positive plate in the last step, packaging is carried out, and the electrode lugs are welded, so that the preparation of the soft-package solid-state battery is finished.
The following will illustrate a specific example of a method for preparing a sulfide all-solid-state lithium battery electrode slice multi-layer laminate sheet according to the present invention, specifically:
1g of LiNi 0.6 Co 0.2 Mn 0.2 O 2 ,0.3g Li 6 PS 5 After adding 5g of cyclohexane to 0.125g of Super P and 0.125g of polyisobutene, stirring for 1h, coating the obtained slurry on aluminum foil, and drying at 120 ℃ to obtain the positive electrode plate of the sulfide all-solid-state battery. Subsequently 0.5g Li 3 InCl 6 After 3g of cyclohexane was added to 0.125g of polyisobutylene and stirred for 1 hour, the above slurry was coated on a positive electrode sheet and dried at 120℃followed by 0.5g of Li 6 PS 5 After adding 4g of cyclohexane into 0.125g of polyisobutene, stirring for 1h, coating the obtained slurry on a positive electrode plate of the prepared sulfide all-solid-state battery, drying at 120 ℃, adding 1g of composite powder of hard carbon and silicon powder with the mass ratio of 5:5 and 0.125g of polyisobutene into 2g of cyclohexane, stirring for 1h, coating the composite powder on a copper-lithium composite belt, drying at 120 ℃, matching the prepared multi-layer laminated sheet with the copper-lithium composite belt, applying 500kg of pressure, and packaging to assemble the sulfide all-solid-state soft-package battery.
As shown in FIG. 1, the multi-layer laminated pole piece constructed by the invention has good flexibility, can still recover a smooth state after being bent, is packaged and welded with a pole lug, and is assembled into a soft package battery for electrochemical performance test. At a charge-discharge rate of 0.1C, as shown in FIG. 2, 230mAh g was maintained in the subsequent 100-week cycle after the activation for the first 20 weeks -1 (782Wh kg -1 ) Has no obvious attenuation trend. The assembled pouch cell was also excellent in high-rate charge and discharge capability at 3C rate, and as shown in fig. 3, was maintained at 120mAh g in the subsequent cycle after the activation for the first 5 weeks -1 Has no obvious decay trend. The results show that the all-solid-state soft package battery assembled by the multi-layer lamination has higher performanceHigh specific discharge capacity, better rate capability, and long cycle performance. And the pole piece is soft, foldable and good in bending property, can be suitable for various scenes, and has good application value.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The electrode plate of the integrated sulfide all-solid-state battery is characterized by comprising a binder, a solvent, a conductive agent, a sulfur silver germanium ore solid-state electrolyte and lithium nickel manganese oxide, wherein the mass ratio of the binder, the solvent, the conductive agent, the sulfur silver germanium ore solid-state electrolyte to the lithium nickel manganese oxide is 1:5:1:3:7.
2. An integrated sulfide all-solid-state battery electrode sheet as claimed in claim 1, wherein said binder comprises one or more of epoxy resin, urethane rubber, polytetrafluoroethylene fiber, polyvinylidene fluoride, polyisobutylene, polymethyl methacrylate, ethyl cellulose.
3. An integrated sulfide all-solid-state battery electrode sheet as claimed in claim 1, wherein said solvent comprises one or more of isobutyl isobutyrate, butyl butyrate, toluene, ethylbenzene, cyclohexane, and n-heptane.
4. An integrated sulfide all-solid-state battery electrode sheet as claimed in claim 1, wherein said conductive agent comprises one or more of Super P, VGCF, acetylene black, ketjen black.
5. The method as claimed in claim 1The integrated sulfide all-solid-state battery electrode plate is characterized in that the chemical formula of the lithium nickel manganese oxide is LiNi 0.6 Co 0.2 Mn 0.2 O 2 。
6. The electrode plate of an integrated sulfide all-solid-state battery as claimed in claim 1, wherein the chemical formula of the sulfur silver germanium ore solid-state electrolyte is Li 6 PS 5 Cl。
7. The method for preparing an integrated sulfide all-solid-state battery electrode slice according to any one of claims 1 to 6, wherein a binder and a solvent are mixed, a conductive agent, lithium nickel manganese oxide and a sulfur silver germanium ore solid electrolyte are added, then stirring is carried out to obtain an electrode slurry, and the electrode slurry is tiled on an aluminum foil and dried to obtain an anode electrode slice; and then mixing the binder, the solvent and the sulfur silver germanium ore solid electrolyte, coating the mixture on the prepared positive electrode plate, drying the mixture, and carrying out multilayer coating.
8. The method for preparing an electrode plate of an integrated sulfide all-solid-state battery according to claim 7, wherein the stirring time of the electrode paste is 1h-10h.
9. The method for preparing an integrated sulfide all-solid-state battery electrode slice according to claim 7, wherein the drying temperature of the electrode slurry is 60-180 ℃.
10. The method for preparing an integrated sulfide all-solid-state battery electrode sheet according to claim 7, wherein the drying temperature of the multilayer coating is 100-130 ℃.
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CN117638268A (en) * | 2024-01-25 | 2024-03-01 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
CN117638268B (en) * | 2024-01-25 | 2024-04-23 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
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