CN115395091A - High-performance composite solid electrolyte membrane and preparation method and application thereof - Google Patents
High-performance composite solid electrolyte membrane and preparation method and application thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 220
- 239000012528 membrane Substances 0.000 title claims abstract description 195
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 42
- 238000000151 deposition Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000012545 processing Methods 0.000 claims description 35
- 229910052786 argon Inorganic materials 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000011863 silicon-based powder Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 19
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- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
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- 239000001301 oxygen Substances 0.000 claims description 10
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- 238000002156 mixing Methods 0.000 claims description 9
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005303 weighing Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 3
- 239000002227 LISICON Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- YWDYRRUFQXZJBG-UHFFFAOYSA-N butyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCOC(=O)C=C YWDYRRUFQXZJBG-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 28
- 239000007787 solid Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 238000005096 rolling process Methods 0.000 description 2
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
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Images
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- 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
-
- 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 high-performance composite solid electrolyte membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) preparing a precursor membrane containing a pore-forming agent; removing the pore-forming agent to prepare a porous solid electrolyte membrane; depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain a high-performance composite solid electrolyte membrane; the support structure of the high-performance composite solid electrolyte membrane prepared by the preparation method is a solid electrolyte material, and a porous structure is formed in the high-performance composite solid electrolyte membrane, so that the high-performance composite solid electrolyte membrane has high ionic conductivity, and can exert high rate performance; the silicon monoxide particles deposited in the pore structure avoid the side reaction of the contact interface of the negative electrode and the electrolyte layer, reduce the loss of irreversible lithium ions and improve the first-week coulombic efficiency of the battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a high-performance composite solid electrolyte membrane and a preparation method and application thereof.
Background
Solid-state batteries have been attracting attention in recent years as next-generation batteries having a large application potential. The solid-state battery adopts non-flammable solid electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, and meanwhile, the battery system can be adapted to the positive electrode and the negative electrode with high capacity, and the improvement of energy density is realized.
The solid electrolyte layer in the current solid-state battery is usually manufactured by adopting a homogenizing and coating process. In the homogenizing step, the solid electrolyte particles are uniformly mixed with a binder and a solvent, and then coated and dried to prepare a continuous electrolyte film. In the process, the solid electrolyte sheet contains a binder, but the binder generally does not have ionic conductivity, so the existence of the binder can influence the ionic conductivity of the solid electrolyte sheet, and the multiplying power and the cycle performance of the battery are reduced. Another method for preparing a binderless solid electrolyte layer is by extrusion molding in a die, which has disadvantages in that a membrane having a large size cannot be prepared due to limitations of a preparation process, and a large pressure extrusion has an influence on a material structure, resulting in a decrease in conductivity. The new preparation method is that a volatilizable binder is added to be coated into a membrane and then the membrane is sintered and formed, but the interface impedance between the solid electrolyte membrane and the anode and the cathode prepared by the method is larger, and finally the battery performance is poorer.
In summary, the existing methods for preparing solid electrolyte sheets all have defects of different degrees, and cannot meet the performance requirements of solid batteries on good contact, better rate capability, better cycle performance and the like of the solid electrolyte sheets, and the problems need to be solved urgently. In view of this, the invention is particularly proposed.
Disclosure of Invention
The embodiment of the invention provides a high-performance composite solid electrolyte membrane and a preparation method and application thereof, wherein a plasma method is used for depositing silicon monoxide in pores on one side of a porous solid electrolyte membrane to prepare the high-performance composite solid electrolyte membrane with the silicon monoxide content distributed in a descending manner in the thickness direction; the composite solid electrolyte membrane is applied to an all-solid-state battery, the first surface with higher content of the silicon monoxide faces to a negative electrode, and the silicon monoxide and a negative electrode plate have better compatibility, so that the first surface of the composite solid electrolyte membrane and the negative electrode plate also have better compatibility, and meanwhile, the silicon monoxide is more uniformly deposited in pores of the solid electrolyte membrane by adopting a plasma method, so that the cycling stability of the material is improved; the second surface with zero content of the silicon monoxide faces the positive electrode, and because the content of the silicon monoxide of the second surface is zero, the interface impedance between the porous solid electrolyte membrane and the positive electrode and the negative electrode is small, and the performance of the battery is further improved.
According to the high-performance composite solid electrolyte membrane provided by the embodiment of the invention, the supporting structure is made of the solid electrolyte material, and the porous structure is formed in the supporting structure, so that the membrane has higher ionic conductivity, and can exert higher rate performance; the silicon monoxide particles deposited in the pore structure avoid the side reaction of the contact interface of the negative electrode and the electrolyte layer, reduce the loss of irreversible lithium ions and improve the first-week coulombic efficiency of the battery.
In a first aspect, an embodiment of the present invention provides a preparation method of a high-performance composite solid electrolyte membrane, where the preparation method includes;
preparing a precursor membrane containing a pore-forming agent;
removing the pore-forming agent to prepare a porous solid electrolyte membrane;
depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain a high-performance composite solid electrolyte membrane;
the preparation method of the precursor membrane containing the pore-forming agent in the step (1) specifically comprises the following steps: weighing solid electrolyte powder, a binder and a pore-forming agent according to a mass ratio, dissolving the mixture in a solvent, uniformly mixing to prepare slurry with the viscosity of 1200-20000 cp, uniformly coating the slurry on the surface of a high-temperature-resistant plate according to the coating thickness of 10-100 μm, placing the high-temperature-resistant plate in an oven, heating to 65-140 ℃, and baking for 15 minutes-2 hours to obtain a precursor membrane containing the pore-forming agent;
the step (2) of removing the pore-forming agent to prepare the porous solid electrolyte membrane specifically comprises the following steps: placing the precursor membrane containing the pore-forming agent in a high-temperature furnace with the oxygen content being more than or equal to 15%, heating to 300-1000 ℃, calcining at high temperature for 0.5-10 hours, and removing the binder and the pore-forming agent to obtain a porous solid electrolyte membrane;
depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by the plasma method in the step (3), and specifically comprises the following steps: placing a high-temperature-resistant plate carrying a porous solid electrolyte membrane in a condensation area of high-frequency plasma processing equipment, placing silicon powder and silicon dioxide powder in a high-temperature area of the high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas to form a plasma high-temperature area with the temperature above 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into the condensation area through carrier gas, depositing the mixed gas into pores on one side of the porous solid electrolyte membrane to grow into silica, and obtaining the high-performance composite solid electrolyte membrane.
Preferably, the mass ratio of the solid electrolyte powder body, the binder and the pore-forming agent is (50-95) to (0.8-20) to (4-60);
the mass ratio of the silicon powder to the silica powder is [ 0.5;
the silicon monoxide is SiO a Wherein a is more than or equal to 0.5 and less than or equal to 1.6.
Preferably, the thickness of the porous solid electrolyte membrane is 5 μm to 90 μm; the pore diameter of the pores of the porous solid electrolyte membrane is between 50nm and 5 mu m, and the porosity is between 30 and 86 percent.
Preferably, the solid electrolyte powder includes: one or more of NASICON type solid electrolyte, LISICON type solid electrolyte, perovskite type solid electrolyte, and garnet type solid electrolyte; the particle size D50 of the solid electrolyte powder is 300nm-30 μm;
the chemical general formula of the NASICON type solid electrolyte is as follows: li 1+x A1 x B1 2-x (PO 4 ) 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.5, A1 is Al, Y, ga, cr, in, fe, Se. One or more La elements, B1 is one or more Ti, ge, ta, zr, sn, fe, V and Hf elements;
the chemical general formula of the LISICON-type solid electrolyte is as follows: li 14-y A2(B2O 4 ) 4 Wherein y is more than or equal to 0 and less than or equal to 8, A2 is one or more of Zr, cr and Sn, and B2 is one or more of Si, S and P;
the chemical general formula of the perovskite type solid electrolyte is as follows: li 3z A3 2/3-z B3O 3 Wherein z is more than or equal to 0.01 and less than or equal to 0.5, A3 is one or more of La, al, mg, fe and Ta, and B3 is one or more of Ti, nb, sr and Pr;
the chemical general formula of the garnet-type solid electrolyte is as follows: li 7 A4 3 B4 2 O 12 Wherein A4 is one or more of La, ca, sr, ba and K, and B4 is one or more of Zr, ta, nb and Hf.
Preferably, the binder comprises: one or more of polyvinylidene fluoride, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene;
the pore-forming agent comprises: one or more of graphite, glucose, sucrose, starch, polystyrene and polymethyl methacrylate; the granularity D50 of the pore-forming agent is 50nm-5 mu m;
the solvent comprises: deionized water, ethanol, N-methylpyrrolidone, isopropanol, ethyl acetate, acetone, and dimethyl carbonate.
Preferably, the working gas comprises: argon or mixed gas of argon and hydrogen, wherein the flow rate of the working gas is 0.5L/min-20L/min;
the carrier gas is argon, and the flow rate of the carrier gas is 0.1L/min-2L/min;
the frequency of the high-frequency plasma processing equipment is between 1MHz and 300 MHz.
In a second aspect, the embodiment of the present invention provides a high-performance composite solid electrolyte membrane prepared by the preparation method described in the first aspect.
Preferably, the thickness of the high-performance composite solid electrolyte membrane is between 5 and 90 μm; the mass percentage of the silicon monoxide in the total mass of the high-performance composite solid electrolyte membrane is 25-80%.
Preferably, one side of the high-performance composite solid electrolyte membrane, which is in contact with the high-temperature resistant plate, is a negative side, and the other side of the high-performance composite solid electrolyte membrane, which is exposed in the atmosphere, is a positive side; the content of the silica on the positive surface is the highest, and the content of the silica on the negative surface is zero.
In a third aspect, embodiments of the present invention provide a lithium battery including the high-performance composite solid-state electrolyte membrane according to the second aspect.
The embodiment of the invention provides a high-performance composite solid electrolyte membrane and a preparation method and application thereof, wherein a plasma method is used for depositing silicon monoxide in pores on one side of a porous solid electrolyte membrane to prepare the high-performance composite solid electrolyte membrane with the silicon monoxide content distributed in a descending manner in the thickness direction; the composite solid electrolyte membrane is applied to an all-solid-state battery, the first surface with higher content of the silicon monoxide faces to a negative electrode, and the silicon monoxide and a negative electrode plate have better compatibility, so that the first surface of the composite solid electrolyte membrane and the negative electrode plate also have better compatibility, and meanwhile, the silicon monoxide is more uniformly deposited in pores of the solid electrolyte membrane by adopting a plasma method, so that the cycling stability of the material is improved; the second surface with zero content of the silicon monoxide faces the positive electrode, and because the content of the silicon monoxide of the second surface is zero, the interface impedance between the porous solid electrolyte membrane and the positive electrode and the negative electrode is small, and the performance of the battery is further improved.
According to the high-performance composite solid electrolyte membrane provided by the embodiment of the invention, the supporting structure is made of the solid electrolyte material, and the porous structure is formed in the supporting structure, so that the membrane has higher ionic conductivity, and can exert higher rate performance; the silicon monoxide particles deposited in the pore structure avoid the side reaction of the contact interface of the negative electrode and the electrolyte layer, reduce the loss of irreversible lithium ions and improve the first-week coulombic efficiency of the battery.
The preparation method of the high-performance composite solid electrolyte membrane provided by the invention has the advantages of simple preparation method and suitability for commercial production.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flow chart of a method for preparing a high-performance composite solid electrolyte membrane according to an embodiment of the present invention.
Fig. 2 is a graph showing discharge capacity at different rates of an all-solid battery assembled with a high-performance composite solid electrolyte membrane prepared in example 1 of the present invention and an all-solid battery assembled with a solid electrolyte membrane prepared in comparative example 1.
Fig. 3 is a charge and discharge graph of an all-solid battery assembled with a high-performance composite solid electrolyte membrane prepared in example 1 of the present invention and an all-solid battery assembled with a solid electrolyte membrane prepared in comparative example 1.
Fig. 4 is a graph showing discharge capacity at different rates of a high-performance composite solid electrolyte membrane-assembled all-solid battery provided in example 2 of the present invention and a composite solid electrolyte membrane-assembled all-solid battery prepared in comparative example 2.
Fig. 5 is a graph showing discharge capacity at different rates of the high-performance composite solid electrolyte membrane-assembled all-solid battery prepared in example 3 of the present invention and the composite solid electrolyte membrane-assembled all-solid battery prepared in comparative example 3.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The embodiment of the invention provides a preparation method of a high-performance composite solid electrolyte membrane, which specifically comprises the following steps as shown in fig. 1.
And step 110, preparing a precursor membrane containing a pore-forming agent.
The method specifically comprises the following steps: weighing solid electrolyte powder, a binder and a pore-forming agent according to a mass ratio, dissolving the mixture in a solvent, uniformly mixing to prepare slurry with the viscosity of 1200-20000 cp, uniformly coating the slurry on the surface of a high-temperature-resistant plate according to the coating thickness of 10-100 μm, placing the high-temperature-resistant plate in an oven, heating to 65-140 ℃, and baking for 15 minutes-2 hours to obtain the precursor membrane containing the pore-forming agent.
Wherein the mass ratio of the solid electrolyte powder body, the binder and the pore-forming agent is [50-95]: 0.8-20]: 4-60], preferably [60-95]: 0.8-10]: 4-50, the mass ratio of the mixture to the solvent is [0.5 ] - [2.5 ].
The application proposes that the viscosity of the slurry is preferably 2000cp to 10000cp, such as 2000cp, 3000cp, 5000cp, 8000cp, 10000cp or any viscosity within the range, that too low a viscosity is not good for controlling the membrane thickness, and too high a viscosity is not good for performing the coating forming process.
The solid electrolyte powder includes: one or more of NASICON type solid electrolyte, LISICON type solid electrolyte, perovskite type solid electrolyte, and garnet type solid electrolyte; the particle size D50 of the solid electrolyte powder is 300nm-30 μm.
The chemical formula of the NASICON type solid electrolyte is as follows: li 1+x A1 x B1 2-x (PO 4 ) 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.5, A1 is one or more of Al, Y, ga, cr, in, fe, se and La, and B1 is one or more of Ti, ge, ta, zr, sn, fe, V and Hf elements.
The chemical formula of the LISICON-type solid electrolyte is as follows: li 14-y A2(B2O 4 ) 4 Wherein y is more than or equal to 0 and less than or equal to 8, A2 is one or more of Zr, cr and Sn, and B2 is one or more of Si, S and P.
The general chemical formula of the perovskite type solid electrolyte is as follows: li 3z A3 2/3-z B3O 3 Wherein z is more than or equal to 0.01 and less than or equal to 0.53 is one or more of La, al, mg, fe and Ta, and B3 is one or more of Ti, nb, sr and Pr.
The chemical formula of the garnet-type solid electrolyte is: li 7 A4 3 B4 2 O 12 Wherein A4 is one or more of La, ca, sr, ba and K, and B4 is one or more of Zr, ta, nb and Hf.
The adhesive comprises: polyvinylidene fluoride, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene.
The pore-forming agent comprises: one or more of graphite, glucose, sucrose, starch, polystyrene and polymethyl methacrylate; the particle size D50 of the pore-forming agent is 50nm-5 mu m.
The solvent comprises: deionized water, ethanol, N-methylpyrrolidone, isopropanol, ethyl acetate, acetone, and dimethyl carbonate.
The application provides that the baking temperature of step 110 should be slightly less than the boiling point temperature of solvent to when avoiding toasting in-process temperature and being higher than solvent boiling point temperature, the solvent is in boiling state and produces the bubble in the diaphragm is inside, can produce uncontrollable hole in the inside of diaphragm, influences the final form of porous solid state electrolyte diaphragm.
And step 120, removing the pore-forming agent to prepare the porous solid electrolyte membrane.
The method specifically comprises the following steps: placing the precursor membrane containing the pore-forming agent in a high-temperature furnace with the oxygen content of more than or equal to 15%, heating to 300-1000 ℃, calcining at high temperature for 0.5-10 hours, and removing the binder and the pore-forming agent to obtain a porous solid electrolyte membrane; wherein the thickness of the porous solid electrolyte membrane is 5-90 μm; the pore diameter of the pores of the porous solid electrolyte membrane is between 50nm and 5 mu m, and the porosity is between 30 and 86 percent.
And step 130, depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain the high-performance composite solid electrolyte membrane.
The method specifically comprises the following steps: placing a high-temperature resistant plate carrying a porous solid electrolyte membrane in a condensation zone of high-frequency plasma processing equipment, placing silicon powder and silicon dioxide powder in a high-temperature zone of the high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas to form a plasma high-temperature zone with the temperature above 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into the condensation zone through carrier gas, depositing the mixed gas into pores on one side of the porous solid electrolyte membrane to grow into silicon protoxide, and obtaining the high-performance composite solid electrolyte membrane.
Wherein the mass ratio of the silicon powder to the silicon dioxide powder is [ 0.5; the working gas comprises: argon or mixed gas of argon and hydrogen, wherein the flow rate of the working gas is 0.5L/min-20L/min; the carrier gas is argon, and the flow rate of the carrier gas is 0.1L/min-2L/min; the frequency of the high-frequency plasma processing apparatus is between 1MHz and 300 MHz.
The thickness of the high-performance composite solid electrolyte membrane prepared by the preparation method is between 5 and 90 mu m; the mass percentage of the silicon monoxide in the total mass of the high-performance composite solid electrolyte membrane is 25-80%; the silicon monoxide being SiO a Wherein a is more than or equal to 0.5 and less than or equal to 1.6.
According to the high-performance composite solid electrolyte membrane provided by the embodiment of the invention, one side, which is in contact with the high-temperature resistant plate, is a negative surface, and the other side, which is exposed in the atmosphere, is a positive surface; the content of the silica on the positive side is the highest, and the content of the silica on the negative side is zero.
The high-performance composite solid electrolyte membrane prepared by the preparation method provided by the embodiment of the invention can be applied to lithium batteries, including but not limited to all-solid-state lithium ion batteries.
In order to better understand the technical scheme provided by the invention, the preparation process and the characteristics of the high-performance composite solid electrolyte membrane are respectively described in the following by using a plurality of specific examples.
Example 1
The embodiment provides a preparation process and a performance test of a high-performance composite solid electrolyte membrane, and the specific steps are as follows.
(1) Preparing a precursor membrane containing a pore-forming agent.
According to the mass ratio of 80:2:18, 20 g of garnet-type solid electrolyte Li having a particle size Dv50 of 2 μm were weighed 7 La 3 Zr 2 O 12 0.5 g of polyvinylidene fluoride, and 4.5 g of graphite powder having a particle size Dv50 of 200 nm.
Polyvinylidene fluoride, graphite powder and solid electrolyte are sequentially added into 20 g of NMP solvent step by step according to the sequence, and each step is uniformly dispersed to prepare slurry with the viscosity of about 3500 cp.
Uniformly coating the slurry on the surface of a high-temperature-resistant plate according to the coating thickness of 60 mu m, placing the high-temperature-resistant plate in a blast drying oven, heating to 100 ℃, and baking for 45 minutes to obtain the precursor membrane containing the pore-forming agent.
(2) And removing the pore-forming agent to prepare the porous solid electrolyte membrane.
And (2) introducing oxygen with the flow rate of 2L/min into the high-temperature furnace, ensuring that the oxygen content in the high-temperature furnace is more than or equal to 15%, then placing the precursor membrane containing the pore-forming agent obtained in the step (1) into the high-temperature furnace, heating to 900 ℃, calcining at high temperature for 2 hours, and removing the binder and the pore-forming agent to obtain the porous solid electrolyte membrane, wherein the thickness of the porous solid electrolyte membrane is 42 microns, the pore size is 130nm-260nm, and the porosity is 39%.
(3) And depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain the high-performance composite solid electrolyte membrane.
Placing a high-temperature resistant plate loaded with a porous solid electrolyte membrane in a condensation area of high-frequency plasma processing equipment, and mixing the components in a mass ratio of 1: putting 50 g of silicon powder and silicon dioxide powder in a high-temperature area of high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas argon to form a plasma high-temperature area with the temperature of more than 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into a condensation area through carrier gas argon, depositing the mixed gas into pores on one side of a porous solid electrolyte membrane to grow into silicon monoxide, and obtaining the high-performance composite solid electrolyte membrane.
The high-performance composite solid electrolyte membrane prepared by the embodiment is used for assembling an all-solid battery for testing, and the preparation and assembly method of the all-solid battery is according to the existing known method and specifically comprises the following steps.
Preparing a positive plate: uniformly mixing a nickel-cobalt-manganese ternary material NCM811, polyvinylidene fluoride PVDF, conductive carbon black SP and N-methyl pyrrolidone NMP in a certain proportion to obtain positive electrode slurry, then coating the positive electrode slurry on an aluminum foil, rolling and cutting the aluminum foil to a proper size, and welding a positive electrode aluminum tab to obtain a positive electrode sheet.
Preparing a negative plate: uniformly mixing a certain proportion of silicon carbon material, sodium carboxymethylcellulose (CMC), conductive carbon black (SP), styrene Butadiene Rubber (SBR) and deionized water to obtain negative electrode slurry, then coating the negative electrode slurry on copper foil, rolling and cutting the copper foil to a proper size, and welding a negative electrode copper nickel-plated tab to obtain a negative electrode sheet.
Assembling an all-solid-state battery: assembling the prepared negative plate, the composite solid electrolyte membrane (the surface with high content of the silica faces the negative plate, and the surface without the silica faces the positive plate) and the positive plate in a staggered and laminated mode, carrying out hot pressing treatment, and carrying out aluminum plastic film negative pressure packaging to obtain the soft package all-solid-state battery.
The electrochemical performance test procedure of the all-solid-state battery is as follows: firstly charging at 0.05C multiplying power for 4.45V, then charging at constant voltage for 4.45V until the current is reduced to 0.01C, then discharging at 0.05C until the voltage is 2.75V, and circulating for 5 circles; charging at 0.1C multiplying power for 4.45V, charging at constant voltage for 4.45V until the current is reduced to 0.02C, discharging at 0.1C until the voltage is 2.75V, and circulating for 5 circles; charging at 0.2C multiplying power for 4.45V, charging at constant voltage for 4.45V until the current is reduced to 0.04C, discharging at 0.2C until the voltage is 2.75V, and circulating for 5 circles; charging at 0.5C multiplying power for 4.45V, charging at constant voltage for 4.45V until the current is reduced to 0.1C, discharging at 0.5C until the voltage is 2.75V, circulating for 5 circles, and ending the test.
The discharge capacity at different rates of the assembled all-solid battery of this example is plotted as shown in fig. 2.
As shown in fig. 3, the charge-discharge curve of the all-solid-state battery assembled in this example shows that the first-week charge capacity of the test battery is 205.08mAh, the discharge capacity is 176.07mAh, and the first-week coulombic efficiency is 85.85%.
Example 2
The embodiment provides a preparation process and a performance test of a high-performance composite solid electrolyte membrane, and the specific steps are as follows.
(1) Preparing a precursor membrane containing a pore-forming agent.
According to the mass ratio of 70:10:20, 14 g of NASICON type solid electrolyte Li with a particle size Dv50 of 700nm were weighed 1.3 Al 0.3 Ti 1.5 Zr 0.2 （PO 4 ) 3 2 g of sodium carboxymethylcellulose and 4 g of graphite powder with a particle size Dv50 of 200 nm.
Sequentially adding sodium carboxymethylcellulose, graphite powder and solid electrolyte into 20 g of deionized water solvent step by step according to the sequence, uniformly dispersing in each step, and preparing into slurry with the viscosity of about 5000 cp.
And uniformly coating the slurry on the surface of a high-temperature resistant plate according to the coating thickness of 50 mu m, placing the high-temperature resistant plate in an oven, heating to 80 ℃, and baking for 30 minutes to obtain the precursor membrane containing the pore-forming agent.
(2) And removing the pore-forming agent to prepare the porous solid electrolyte membrane.
And (2) introducing air with the flow rate of 4L/min into the high-temperature furnace to ensure that the oxygen content in the high-temperature furnace is more than or equal to 15%, then placing the precursor membrane containing the pore-forming agent obtained in the step (1) into the high-temperature furnace, heating to 900 ℃, calcining at high temperature for 3 hours, and removing the binder and the pore-forming agent to obtain the porous solid electrolyte membrane, wherein the thickness of the porous solid electrolyte membrane is 40 microns, the pore size is 130nm-260nm, and the porosity is 40%.
(3) And depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain the high-performance composite solid electrolyte membrane.
Placing a high-temperature resistant plate loaded with a porous solid electrolyte membrane in a condensation area of high-frequency plasma processing equipment, and mixing the components in a mass ratio of 0.5: the method comprises the following steps of 1, putting 50 g of silicon powder and silicon dioxide powder in total into a high-temperature area of high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas argon to form a plasma high-temperature area with the temperature above 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into a condensation area through carrier gas argon, depositing the mixed gas into pores on one side of a porous solid electrolyte membrane to grow into silica, and obtaining the high-performance composite solid electrolyte membrane.
The high-performance composite solid electrolyte membrane prepared in this example was used to assemble an all-solid-state battery, and the assembly process and test method were the same as those of example 1.
The discharge capacity at different rates of the assembled all-solid battery of this example is plotted as shown in fig. 4.
The initial charge capacity of the all-solid battery assembled in this example was 203.454mAh, the discharge capacity was 175.011mAh, and the initial coulombic efficiency was 86.02%.
Example 3
The embodiment provides a preparation process and a performance test of a high-performance composite solid electrolyte membrane, and the specific steps are as follows.
(1) Preparing a precursor membrane containing a pore-forming agent.
According to the mass ratio of 60:8:32, 15 g of NASICON type solid electrolyte Li with a particle size Dv50 of 700nm were weighed 1.5 Al 0.5 Ge 1.5 （PO 4 ) 3 2 g of polyvinylidene fluoride, and 8 g of starch having a particle size Dv50 of 100 nm.
Polyvinylidene fluoride, starch and solid electrolyte are sequentially added into 25 g of NMP solvent step by step according to the sequence, and each step is uniformly dispersed to prepare slurry with the viscosity of about 3000 cp.
Uniformly coating the slurry on the surface of a high-temperature resistant plate according to the coating thickness of 80 mu m, putting the high-temperature resistant plate in an oven, heating to 105 ℃, and baking for 1 hour to obtain a precursor membrane containing the pore-forming agent.
(2) And removing the pore-forming agent to prepare the porous solid electrolyte membrane.
And (2) introducing air with the flow rate of 4L/min into the high-temperature furnace to ensure that the oxygen content in the high-temperature furnace is more than or equal to 15%, then placing the precursor membrane containing the pore-forming agent obtained in the step (1) into the high-temperature furnace, heating to 800 ℃, calcining at high temperature for 3 hours, and removing the binder and the pore-forming agent to obtain the porous solid electrolyte membrane, wherein the thickness of the porous solid electrolyte membrane is 62 microns, the pore size is 76nm-160nm, and the porosity is 52%.
(3) And depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain the high-performance composite solid electrolyte membrane.
Placing a high-temperature resistant plate loaded with a porous solid electrolyte membrane in a condensation area of high-frequency plasma processing equipment, and mixing the components in a mass ratio of 2: putting 50 g of silicon powder and silicon dioxide powder in a high-temperature area of high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas argon to form a plasma high-temperature area with the temperature of more than 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into a condensation area through carrier gas argon, depositing the mixed gas into pores on one side of a porous solid electrolyte membrane to grow into silicon monoxide, and obtaining the high-performance composite solid electrolyte membrane.
The test was carried out by assembling an all-solid battery using the solid electrolyte membrane prepared in this example as an electrolyte layer. The specific assembly process and test conditions were the same as in example 1.
The discharge capacity at different rates of the assembled all-solid battery of this example is plotted as shown in fig. 5.
The all-solid-state battery assembled in the embodiment has the first-week charge capacity of 202.210mAh, the discharge capacity of 172.132mAh and the first-week coulombic efficiency of 85.13%.
Example 4
The embodiment provides a preparation process and a performance test of a high-performance composite solid electrolyte membrane, which specifically comprises the following steps.
(1) Preparing a precursor membrane containing a pore-forming agent.
According to the mass ratio of 85:5:10, 25.5 g of a perovskite solid electrolyte Li having a particle size Dv50 of 5 μm was weighed 0.35 La 0.55 TiO 3 1.5 g of polyvinyl acetate, and 3 g of polystyrene powder having a particle size Dv50 of 500 nm.
Polyvinyl acetate, polystyrene powder and solid electrolyte are sequentially added into 22 g of ethanol solvent step by step according to the sequence, and each step is uniformly dispersed to prepare slurry with the viscosity of about 6000 cp.
Uniformly coating the slurry on the surface of a high-temperature resistant plate according to the coating thickness of 60 mu m, placing the high-temperature resistant plate in a baking oven, heating to 70 ℃, and baking for 30 minutes to obtain a precursor membrane containing the pore-forming agent.
(2) And removing the pore-forming agent to prepare the porous solid electrolyte membrane.
And (2) introducing oxygen with the flow rate of 1.5L/min into the high-temperature furnace, ensuring that the oxygen content in the high-temperature furnace is more than or equal to 15%, then placing the precursor membrane containing the pore-forming agent obtained in the step (1) into the high-temperature furnace, heating to 850 ℃, calcining at high temperature for 4 hours, and removing the binder and the pore-forming agent to obtain the porous solid electrolyte membrane, wherein the thickness of the porous solid electrolyte membrane is 45 microns, the pore size is 420nm-570nm, and the porosity is 55%.
(3) And depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain the high-performance composite solid electrolyte membrane.
Placing a high-temperature resistant plate loaded with a porous solid electrolyte membrane in a condensation area of high-frequency plasma processing equipment, and mixing the components in a mass ratio of 0.8: putting 72 g of silicon powder and silicon dioxide powder in a high-temperature area of high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas argon to form a plasma high-temperature area with the temperature of more than 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into a condensation area through carrier gas argon, depositing the mixed gas into pores on one side of a porous solid electrolyte membrane to grow into silicon monoxide, and obtaining the high-performance composite solid electrolyte membrane.
The solid electrolyte membrane prepared in this example was used as an electrolyte layer to assemble an all-solid battery and the specific assembly process and test conditions were the same as those of example 1.
The all-solid-state battery assembled in the embodiment has the first-cycle charge capacity of 203.343mAh, the discharge capacity of 174.055mAh and the first-cycle coulombic efficiency of 85.60%.
To better illustrate the effects of the examples of the present invention, comparative examples 1 to 3 were compared with examples 1 to 3, respectively.
Comparative example 1
The comparative example provides a preparation process and performance test of a solid electrolyte membrane, and is different from example 1 in that pore-forming is not carried out and silicon monoxide deposition is not carried out, and the specific preparation steps are as follows.
(1) Weighing 0.5 g of polyvinylidene fluoride powder, fully stirring and dissolving the polyvinylidene fluoride powder into NMP solvent, and then adding 20 g of garnet type solid electrolyte Li with the particle size Dv50 of 2 mu m 7 La 3 Zr 2 O 12 Stirring and dispersing, adjusting the viscosity of the slurry to be 3500cp, then adjusting the thickness of a scraper to be 60 μm, coating the slurry on the surface of a high-temperature resistant flat plate, and transferring the flat plate to a 100 ℃ blast drying oven to bake for 45 minutes to obtain a precursor membrane.
(2) And (3) placing the obtained precursor membrane in a high-temperature furnace, introducing oxygen at the gas flow rate of 2L/min, sintering at the temperature of 900 ℃ for 2 hours, and removing the polyvinylidene fluoride binder to obtain the solid electrolyte membrane.
An all-solid battery was assembled in the same manner as in example 1 using the solid electrolyte membrane sheet prepared in this comparative example, and was tested under the test conditions of example 1.
As shown in fig. 2, it can be seen that the capacity of comparative example 1 is significantly smaller than that of example 1 under the high rate current condition, and the larger the current, the faster comparative example 1 decays.
As shown in fig. 3, it can be seen from the charge and discharge curves of the all-solid battery of the comparative example that the first cycle charge capacity of the all-solid battery of the comparative example is 209.187mAh, the discharge capacity is 174.759mAh, the first cycle coulombic efficiency is 83.54%, and the first cycle coulombic efficiency of example 1 is higher than that of comparative example 1.
Comparative example 2
The comparative example provides a preparation process and a performance test method of a composite porous solid electrolyte membrane, and is different from the example 2 in that nano silicon particles are deposited in pores of the porous solid electrolyte membrane, and the specific steps are as follows.
(1) The process for preparing the precursor membrane containing the pore-forming agent was the same as in example 2.
(2) The procedure for preparing a porous solid electrolyte membrane by removing the pore-forming agent was the same as in example 2.
(3) Placing a high-temperature resistant plate carrying a porous solid electrolyte membrane in a condensation zone of high-frequency plasma processing equipment, placing 50 g of industrial silicon powder in a high-temperature zone of the high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas argon to form a plasma high-temperature zone with the temperature of more than 5000K, gasifying and dissociating the industrial silicon powder to form silicon-containing gas, carrying the silicon-containing gas into the condensation zone through carrier gas argon, depositing the silicon-containing gas into pores on one side of the porous solid electrolyte membrane to grow into nano silicon particles, and obtaining the composite solid electrolyte membrane.
An all-solid battery was assembled in the same manner as in example 1 using the composite solid electrolyte membrane sheet prepared in this comparative example, and was tested under the test conditions of example 1.
As shown in fig. 4, it can be seen that the capacity of comparative example 2 is significantly smaller than that of example 2 under the high rate current condition, and the larger the current, the faster comparative example 2 decays.
The first cycle charge capacity of the all-solid-state battery of this comparative example was 211.967mAh, the discharge capacity was 175.763mAh, and the first cycle coulombic efficiency was 82.92%.
Comparative example 3
The comparative example provides a preparation process and a performance test method of a composite porous solid electrolyte membrane, and is different from example 3 in that the comparative example adopts a conventional chemical vapor deposition method to deposit silicon monoxide into pores of the porous solid electrolyte membrane, and the specific steps are as follows.
(1) The process for preparing the precursor membrane containing the pore-forming agent was the same as in example 3.
(2) The procedure for preparing a porous solid electrolyte membrane by removing the pore-forming agent was the same as in example 3.
(3) Depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a chemical vapor deposition method to obtain the composite solid electrolyte membrane, which comprises the following specific steps.
1kg of silicon powder and 1.5kg of micron-sized silicon dioxide powder are uniformly mixed, placed in a vacuum furnace, vacuumized to 50Pa, heated to 1600 ℃ and subjected to centering reaction to obtain gas of silicon monoxide.
And placing the high-temperature-resistant plate containing the porous solid electrolyte membrane in a deposition chamber of a vapor deposition furnace, introducing protective gas argon into the deposition chamber to replace air, heating the deposition chamber to 900 ℃, introducing silicon monoxide gas into the deposition chamber, cooling the silicon monoxide gas, and depositing the silicon monoxide gas in pores of the porous solid electrolyte membrane to obtain the composite solid electrolyte membrane.
An all-solid battery was assembled in the same manner as in example 1 using the composite solid electrolyte membrane sheet prepared in this comparative example, and was tested under the test conditions of example 1.
As shown in fig. 5, the capacity of the all-solid-state battery of the comparative example is obviously smaller than that of the example 3 under the condition of high-rate current, and the larger the current is, the faster the attenuation of the comparative example 3 is; the first cycle efficiency of the cell of comparative example 3 is lower than that of the cell of example 3, because the rate performance is better because the plasma method adopted in example 3 makes the deposition of the silicon oxide more uniform and dense compared with the traditional vapor deposition method of comparative example 3.
The comparative example all-solid-state battery tests that the first-week charge capacity is 205.316mAh, the discharge capacity is 170.453mAh, and the first-week coulombic efficiency is 83.02%.
The embodiment of the invention provides a high-performance composite solid electrolyte membrane and a preparation method and application thereof, wherein a plasma method is used for depositing silicon monoxide in pores on one side of a porous solid electrolyte membrane to prepare the high-performance composite solid electrolyte membrane with the silicon monoxide content distributed in a descending manner in the thickness direction; the composite solid electrolyte membrane is applied to an all-solid-state battery, the first surface with higher content of the silicon monoxide faces to a negative electrode, and the silicon monoxide and a negative electrode plate have better compatibility, so that the first surface of the composite solid electrolyte membrane and the negative electrode plate also have better compatibility, and simultaneously, the silicon monoxide is more uniformly deposited in pores of the solid electrolyte membrane by adopting a plasma method, so that the circulation stability of the material is improved; the second surface with zero content of the silicon monoxide faces the positive electrode, and because the content of the silicon monoxide of the second surface is zero, the interface impedance between the porous solid electrolyte membrane and the positive electrode and the negative electrode is small, and the performance of the battery is further improved.
According to the high-performance composite solid electrolyte membrane provided by the embodiment of the invention, the supporting structure is made of the solid electrolyte material, and the porous structure is formed in the supporting structure, so that the membrane has higher ionic conductivity, and can exert higher rate performance; the silicon monoxide particles deposited in the pore structure avoid the side reaction of the contact interface of the negative electrode and the electrolyte layer, reduce the loss of irreversible lithium ions and improve the first-week coulombic efficiency of the battery.
The preparation method of the high-performance composite solid electrolyte membrane provided by the invention has the advantages of simple preparation method and suitability for commercial production.
The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-performance composite solid electrolyte membrane is characterized by comprising the following steps of;
preparing a precursor membrane containing a pore-forming agent;
removing the pore-forming agent to prepare a porous solid electrolyte membrane;
depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by a plasma method to obtain a high-performance composite solid electrolyte membrane;
the preparation method of the precursor membrane containing the pore-forming agent in the step (1) specifically comprises the following steps: weighing solid electrolyte powder, a binder and a pore-forming agent according to a mass ratio, dissolving the mixture in a solvent, uniformly mixing to prepare slurry with the viscosity of 1200-20000 cp, uniformly coating the slurry on the surface of a high-temperature-resistant plate according to the coating thickness of 10-100 μm, placing the high-temperature-resistant plate in an oven, heating to 65-140 ℃, and baking for 15 minutes-2 hours to obtain a precursor membrane containing the pore-forming agent;
the step (2) of removing the pore-forming agent to prepare the porous solid electrolyte membrane specifically comprises the following steps: placing the precursor membrane containing the pore-forming agent in a high-temperature furnace with the oxygen content being more than or equal to 15%, heating to 300-1000 ℃, calcining at high temperature for 0.5-10 hours, and removing the binder and the pore-forming agent to obtain a porous solid electrolyte membrane;
depositing the silicon monoxide into the pores on one side of the porous solid electrolyte membrane by the plasma method in the step (3), and specifically comprises the following steps: placing a high-temperature resistant plate carrying a porous solid electrolyte membrane in a condensation zone of high-frequency plasma processing equipment, placing silicon powder and silicon dioxide powder in a high-temperature zone of the high-frequency plasma processing equipment, introducing protective gas argon into the high-frequency plasma processing equipment to replace air, starting a plasma generator of the high-frequency plasma processing equipment, ionizing working gas to form a plasma high-temperature zone with the temperature above 5000K, gasifying and dissociating the silicon powder and the silicon dioxide powder to form mixed gas, carrying the mixed gas into the condensation zone through carrier gas, depositing the mixed gas into pores on one side of the porous solid electrolyte membrane to grow into silicon protoxide, and obtaining the high-performance composite solid electrolyte membrane.
2. The method for preparing a high-performance composite solid electrolyte membrane as claimed in claim 1, wherein the mass ratio of the solid electrolyte powder body, the binder and the pore-forming agent is [50-95]: 0.8-20]: 4-60];
the mass ratio of the silicon powder to the silica powder is [ 0.5;
the silicon monoxide is SiO a Wherein a is more than or equal to 0.5 and less than or equal to 1.6.
3. The method for producing a high-performance composite solid electrolyte membrane according to claim 1, wherein the porous solid electrolyte membrane has a thickness of 5 μm to 90 μm; the pore diameter of the pores of the porous solid electrolyte membrane is between 50nm and 5 mu m, and the porosity is between 30 and 86 percent.
4. The method of producing a high-performance composite solid electrolyte membrane according to claim 1, wherein the solid electrolyte powder comprises: one or more of NASICON type solid electrolyte, LISICON type solid electrolyte, perovskite type solid electrolyte, and garnet type solid electrolyte; the particle size D50 of the solid electrolyte powder is 300nm-30 μm;
the chemical general formula of the NASICON type solid electrolyte is as follows: li 1+x A1 x B1 2-x (PO 4 ) 3 Wherein x is more than or equal to 0.01 and less than or equal to 0.5, A1 is one or more of Al, Y, ga, cr, in, fe, se and La, and B1 is one or more of Ti, ge, ta, zr, sn, fe, V and Hf elements;
the chemical general formula of the LISICON-type solid electrolyte is as follows: li 14-y A2(B2O 4 ) 4 Wherein y is more than or equal to 0 and less than or equal to 8, A2 is one or more of Zr, cr and Sn, B2 is Si, S,One or more of P;
the chemical general formula of the perovskite type solid electrolyte is as follows: li 3z A3 2/3-z B3O 3 Wherein z is more than or equal to 0.01 and less than or equal to 0.5, A3 is one or more of La, al, mg, fe and Ta, and B3 is one or more of Ti, nb, sr and Pr;
the chemical general formula of the garnet-type solid electrolyte is as follows: li 7 A4 3 B4 2 O 12 Wherein A4 is one or more of La, ca, sr, ba and K, and B4 is one or more of Zr, ta, nb and Hf.
5. The method of manufacturing a high performance composite solid electrolyte membrane according to claim 1, wherein the binder comprises: one or more of polyvinylidene fluoride, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene;
the pore-forming agent comprises: one or more of graphite, glucose, sucrose, starch, polystyrene and polymethyl methacrylate; the granularity D50 of the pore-forming agent is 50nm-5 mu m;
the solvent comprises: deionized water, ethanol, N-methylpyrrolidone, isopropanol, ethyl acetate, acetone, and dimethyl carbonate.
6. The method of manufacturing a high performance composite solid electrolyte membrane according to claim 1, wherein the working gas comprises: argon or a mixed gas of argon and hydrogen, wherein the flow rate of the working gas is 0.5L/min-20L/min;
the carrier gas is argon, and the flow rate of the carrier gas is 0.1L/min-2L/min;
the frequency of the high-frequency plasma processing equipment is between 1MHz and 300 MHz.
7. A high-performance composite solid electrolyte membrane prepared by the preparation method of any one of claims 1 to 6.
8. The high performance composite solid electrolyte membrane of claim 7, wherein said high performance composite solid electrolyte membrane has a thickness of between 5 μm and 90 μm; the mass percentage of the silicon monoxide in the total mass of the high-performance composite solid electrolyte membrane is 25-80%.
9. The high-performance composite solid electrolyte membrane according to claim 7, wherein one side of the high-performance composite solid electrolyte membrane, which is in contact with the high-temperature resistant plate, is a negative side, and the other side of the high-performance composite solid electrolyte membrane, which is exposed to the atmosphere, is a positive side; the content of the silica on the positive surface is the highest, and the content of the silica on the negative surface is zero.
10. A lithium battery comprising the high-performance composite solid electrolyte membrane according to claim 7.
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