CN112151764A - Electrode plate and preparation method and application thereof - Google Patents

Electrode plate and preparation method and application thereof Download PDF

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Publication number
CN112151764A
CN112151764A CN202010916422.9A CN202010916422A CN112151764A CN 112151764 A CN112151764 A CN 112151764A CN 202010916422 A CN202010916422 A CN 202010916422A CN 112151764 A CN112151764 A CN 112151764A
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electrolyte
electrode material
electrode
solid electrolyte
preparation
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许晓雄
张永龙
魏引利
陈董亮
吴云峰
丁超
徐礼虎
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Zhejiang Funlithium New Energy Tech Co Ltd
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Zhejiang Funlithium New Energy Tech Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 an electrode plate and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing an electrode material pole piece, namely stirring an electrode material, a conductive agent, an adhesive, a dispersing agent and a pore-forming agent to prepare slurry, coating the slurry on the surface of a current collector, and drying to obtain the electrode material pole piece; electrolyte solution preparation: carrying out mechanical ball milling on the solid electrolyte to obtain electrolyte powder, and dissolving the electrolyte powder in an organic solvent to obtain an electrolyte solution; preparing an electrode plate: the electrode pole piece of the solid-state lithium ion battery is prepared by the preparation method, and the prepared electrode pole piece is applied to any one of the traditional liquid-state lithium battery, the polymer lithium battery, the mixed solid-liquid electrolyte lithium storage battery and the solid-state battery. The invention has the advantages of low cost in the preparation process and easy mass production, and the prepared electrode plate has excellent electrochemical performance.

Description

Electrode plate and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrode plate and a preparation method and application thereof.
Background
Lithium ion batteries have the advantages of high energy density, high working voltage, no memory effect and the like, and are currently and generally applied to daily portable electronic products, power batteries and energy storage systems. The traditional lithium ion battery adopts organic electrolyte as a carrier for lithium ion transmission, but when the temperature rises, the electrolyte and materials in a battery system generate a series of side reactions, so that the internal resistance of the battery is obviously increased, gas generation and other phenomena can be accompanied, and the safety and the usability of the battery are seriously threatened. In order to solve the above problems of the conventional lithium ion battery, a solid electrolyte is generally used as a lithium ion transport carrier, and the solid electrolyte is non-volatile, non-flammable, free of liquid leakage and excellent in thermal stability and safety. And some inorganic solid electrolytes also have high-strength mechanical properties, so that the 'lithium dendrite' can be effectively prevented from penetrating through the electrolytes, and the advantage of the inorganic solid electrolytes enables the lithium metal to be used as a negative electrode of the battery, so that the energy density of the battery can be greatly improved. Although solid-state batteries have significant advantages in safety and energy density, their development still faces some problems, and in all-solid-state systems, since the solid-state electrolyte and the electrode material belong to solid-solid contact, the interface resistance is large, resulting in a drastic drop in battery performance.
In order to alleviate the problems, Atomic Layer Deposition (ALD) is mostly adopted to prepare modified solid electrolyte or dry mechanical ball milling is carried out on electrode material active substances, electrolyte, carbon materials and the like, the preparation method for preparing the solid electrolyte by the deposition method is high in cost, and samples for uniformly coating the electrolyte are difficult to obtain only by mechanical ball milling, so that the preparation method which is low in cost, easy for large-scale production and excellent in electrochemical performance is especially important to find.
Disclosure of Invention
In view of the defects in the prior art, the first object of the present invention is to provide a method for preparing an electrode plate, which has the advantages of low cost in the preparation process, easy mass production, and excellent electrochemical performance of the prepared electrode plate.
A second object of the present invention is to provide an electrode sheet having an advantage of excellent electrochemical properties.
The third purpose of the present invention is to provide an application of the electrode plate, which has the advantage of wide application range.
In order to achieve the first object, the invention provides the following technical scheme: a preparation method of an electrode plate comprises the following steps:
preparing an electrode material pole piece, namely stirring an electrode material, a conductive agent, an adhesive, a dispersing agent and a pore-forming agent to prepare slurry, coating the slurry on the surface of a current collector, and drying to obtain the electrode material pole piece;
electrolyte solution preparation: carrying out mechanical ball milling on the solid electrolyte to obtain electrolyte powder, and dissolving the electrolyte powder in an organic solvent to obtain an electrolyte solution;
preparing an electrode plate: and soaking the electrode material pole piece in an electrolyte solution, heating and drying, and tabletting to obtain the electrode pole piece.
By adopting the technical scheme, the pore-forming agent is added into the electrode material, then the slurry is coated on the current collector and dried, the pore-forming agent is decomposed along with the rise of temperature, so that the electrode material pole piece has a loose porous structure, then the electrode material pole piece with the porous structure is soaked in the liquid electrolyte solution, the soaking of the electrolyte solution on the electrode material pole piece is facilitated, and then the electrode pole piece is prepared by solidification, the electrode pole piece prepared by the preparation method improves the contact area between the electrode material and the electrolyte, reduces the interface resistance between the electrode material and the electrolyte, greatly simplifies the preparation process of the solid-state battery, reduces the production cost, improves the preparation efficiency of the solid-state battery, and has excellent electrochemical performance, excellent cycle life and rate performance, the internal resistance of the battery is reduced. The pole piece with higher compaction density is obtained by tabletting operation, which is beneficial to improving the volume energy density of the battery.
The invention is further configured to: in the step of preparing the electrode material pole piece, the preparation method of the slurry comprises the following steps of: dissolving 90-96 parts of electrode material, 0.1-5.0 parts of conductive agent, 1.0-3.0 parts of adhesive and 5-20 parts of pore-forming agent in dispersing agent to prepare slurry with solid content of 40-70%.
By adopting the technical scheme, a large number of experiments prove that the electrode plate prepared by selecting the conductive agent, the pore-forming agent and the like in the proportion is of a porous structure, the mutually-crosslinked pore frame structure provides a rapid channel for electron transfer, and after the electrode plate is soaked by the electrolyte solution, the conductivity of lithium ions is improved by the electrode plate of the porous structure.
The invention is further configured to: in the step of preparing the electrode material pole piece, the electrode material is a positive electrode material or a negative electrode material, and the positive electrode material is selected from lithium cobaltate Li1+zCo1-nAnO2Ternary material Li1+zNixCoyM1-x-y-nAnO2Lithium-rich manganese mLi2MnO3·(1-m)Li1+zNixCoyMn1-x-y-n AnO2Ni-Mn spinel Li1+zNi0 .5-hMn1 .5-lAnO4Lithium iron manganese phosphate Li1+zFexMn1-x-nAnPO4Lithium manganate Li1+zMn2-nAnO4Lithium iron phosphate Li(1+z)Fe(1-n)AnPO4Wherein, z is more than or equal to 0 and less than 0.1, n is more than or equal to 0 and less than 0.1, x is more than 0 and less than 1, y is more than 0 and less than 1, x + y + n is more than 0 and less than 1, M is more than 0 and less than 1, h + l is n, M is Mn or Al, A is at least one element of Ti, Mg, Al, Zr, Nb, Ba, La, V, W, Ag and Sn, preferably lithium cobaltate Li1+zCo1-nAnO2Ternary material Li1+zNixCoyM1-x-y-nAnO2And lithium iron phosphate Li(1+z)Fe(1-n)AnPO4；
The negative electrode material is selected from one or more of artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads, metallic lithium, Li-C compounds, lithium alloys, transition metal oxides and lithium titanate, preferably a carbon negative electrode material such as artificial graphite, natural graphite, soft carbon, hard carbon and mesocarbon microbeads, and more preferably artificial graphite.
By adopting the technical scheme, the inventor conducts a large number of experiments, and when the anode electrode material is made of the ternary material, the ternary material has higher energy density, good high-low temperature performance and stable cycle performance although the first coulombic efficiency is lower than that of lithium cobaltate and lithium manganate.
The invention is further configured to: in the step of preparing the electrode material pole piece, the conductive agent is selected from one or more of carbon nano tube, carbon black, graphene and Keqin black;
the binding agent is selected from one or more of polyvinylidene fluoride, polyvinyl alcohol, styrene butadiene rubber, sodium carboxymethylcellulose, polyacrylic acid, polyacrylonitrile, nitrile butadiene rubber and silica gel, and is preferably polyvinylidene fluoride when the electrode pole piece is a positive pole piece, and is preferably polyvinylidene fluoride, sodium carboxymethylcellulose and styrene butadiene rubber when the electrode pole piece is a negative pole piece.
The dispersing agent is selected from one or more of N-methyl pyrrolidone, water, toluene or xylene;
the pore-forming agent is one or more of oxalic acid, citric acid or benzoic acid, preferably oxalic acid.
By adopting the scheme, the pore-forming agent can release gas such as carbon dioxide after being heated, the pore-forming agent selected in the invention is added in the preparation process of the electrode material pole piece, and then the pore-forming agent releases gas in the drying process after being coated on the current collector, and the gas overflows in the electrode material pole piece to generate a hole structure.
The invention is further configured to: in the step of preparing the electrode material pole piece, the slurry is coated on the surface of a current collector, the drying temperature is 60-130 ℃, the drying time is 0.5-2h, and the coating amount is 1-100mg/cm2；
The current collector is copper foil, aluminum foil, foamed nickel or other substances which can bear materials and have good conductivity.
The invention is further configured to: in the step of preparing the electrolyte solution, the solid electrolyte is a solid polymer electrolyte or an inorganic solid electrolyte, and the organic solvent is selected from one or more of acetonitrile, N-methyl amide, acetone, toluene, tetrahydrofuran, butyl butyrate, N-methyl pyrrolidone, N-heptane and ethanol;
the mass ratio of the organic solvent to the electrolyte powder is (5-15) to 1;
the solid electrolyte is a polymer electrolyte or an inorganic solid electrolyte;
the polymer electrolyte is composed of a polymer matrix and lithium salt, the polymer body is selected from one or more of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylidene chloride and single-ion polymer electrolyte, and the lithium salt is LiClO4、LiAsF4、LiPF6、LiBF4One or more of;
the inorganic solid electrolyte comprises one or two of an oxide solid electrolyte and a sulfide solid electrolyte, wherein the oxide solid electrolyte is selected from one of a garnet solid electrolyte material, an NASICON solid electrolyte material, a LISICON solid electrolyte material, a perovskite solid electrolyte material and a derivative material thereof, and the derivative material of the oxide solid electrolyte comprises one or a mixture of more of the garnet solid electrolyte material, the NASICON solid electrolyte material, the LISICON solid electrolyte material and the perovskite solid electrolyte material, and is obtained by doping or coating;
the sulfide-type solid electrolyte is crystalline or amorphous Li2S-P2S5Crystalline form of Li4MS4Crystalline form of Li10NP2S12Microcrystalline Li2S-P2S5-one or more of LiX and derived materials thereof; wherein M is selected from one or more of Si, Ge and Sn, N is selected from one or more of Si, Ge and Sn, X is selected from one or more of Cl, Br and I, 0 < X < 1, and the derivative material of the sulfide type solid electrolyte comprises binary sulfide Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3And ternary sulfide Li2S-MeS2-P2S5The one or more than one of the above components are doped or coated, wherein Me is selected from one of Si, Ge, Sn and Al.
The invention is further configured to: in the step of preparing the electrolyte solution, wet mechanical ball milling is adopted for mechanical ball milling, acetonitrile or absolute ethyl alcohol is adopted as a medium for wet ball milling, and the mass ratio of the solid electrolyte, the balls and the acetonitrile or absolute ethyl alcohol is 1 (0.8-1.5): (0.8-1.2), the ball milling speed is 100 and 1000rpm, and the ball milling time is 0.5-20 h.
By adopting the technical scheme, the solid electrolyte can be well crushed in the ball milling process by wet ball milling, the particles are prevented from being aggregated, the contact area of the electrode material and the electrolyte is increased, and the interface resistance between the electrode material and the electrolyte is reduced.
The invention is further configured to: in the step of preparing the electrode pole piece, when the electrode pole piece is soaked in an electrolyte solution, the soaking time is 0.5-10h, heating and drying are carried out under the vacuum condition, the heating temperature is 80-200 ℃, the heating time is 0.5-10h, and further, when heating and drying are carried out, the electrode pole piece is firstly dried under an inert environment to volatilize a solvent, and then is dried under the vacuum condition.
In order to achieve the second object, the invention provides the following technical scheme, and the electrode plate of the solid-state lithium ion battery is prepared by the method.
In order to achieve the third object, the present invention provides a technical solution that the electrode plate is applied to any one of a conventional liquid lithium battery, a polymer lithium battery, a mixed solid-liquid electrolyte lithium battery, and a solid lithium battery.
By adopting the technical scheme, the electrode plate prepared by the method is applied to the traditional liquid lithium battery and polymer battery, and the solid electrolyte plays the roles of stabilizing the electrode material structure, inhibiting the expansion effect of the electrode plate in the circulating process and increasing the ion transmission efficiency, so that the circulating life of the battery can be prolonged, and the rate capability and the safety performance of the battery can be improved; the prepared electrode plate is applied to a mixed solid-liquid electrolyte lithium storage battery and a solid-state battery, and besides the advantages, the electrode plate can increase the interface contact between the electrode material plate and an electrolyte solution, reduce the interface resistance, and achieve the effects of reducing the internal resistance of the battery, prolonging the cycle life and improving the rate capability. The electrode plate prepared by the method can be applied to various lithium batteries, and has a wide application range.
In conclusion, the invention has the following beneficial effects:
1. the preparation method can greatly simplify the preparation process of the solid-state battery, improve the preparation efficiency of the solid-state battery and reduce the production cost, and meanwhile, the prepared electrode plate has excellent electrochemical performance, excellent cycle life and rate performance and reduces the internal resistance of the battery;
2. according to the invention, the porous electrode material pole piece is soaked in the solid electrolyte solution and then is solidified, so that the contact area of the electrode material pole piece and the electrolyte solution is increased, the interface resistance is reduced, the porous electrode material pole piece has a larger specific surface area, the effective load of the electrolyte can be realized while the capacity of the electrode material is not reduced, the porous structure is favorable for soaking the electrolyte solution, after the electrode material pole piece is completely soaked by the electrolyte solution, the porous gap is favorable for providing the transmission capability of lithium ions, and the prepared electrode pole piece has excellent lithium ion conductivity;
3. the electrode pole piece prepared by the method has the advantages of stabilizing the electrode material structure, inhibiting the expansion effect of the electrode pole piece in the circulation process, increasing the ion transmission efficiency and reducing the interface resistance, and the finally prepared electrode pole piece can prolong the circulation life of the battery and improve the rate capability and the safety performance of the battery when being used in the traditional liquid lithium battery, the polymer battery, the mixed solid-liquid electrolyte lithium storage battery and the solid battery.
Drawings
FIG. 1 is a simple schematic diagram of the preparation of the electrode material provided by the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
The invention provides a preparation method of an electrode plate, which comprises the following steps as shown in figure 1:
preparing an electrode material pole piece: dissolving 90-96 parts of electrode material, 0.1-5.0 parts of conductive agent, 1.0-4.0 parts of adhesive and 1.0-4.0 parts of pore-forming agent in a dispersing agent by weight parts to prepare slurry with the solid content of 40-70%, coating the slurry on the surface of a current collector, and then coating the slurry with the coating amount of 1-100mg/cm2Drying at 60-130 ℃ for 0.5-2h to obtain an electrode material pole piece;
electrolyte solution preparation: carrying out mechanical wet ball milling on 40-55 g of solid electrolyte to obtain electrolyte powder, wherein acetonitrile or absolute ethyl alcohol is selected as a wet ball milling medium, and the mass ratio of the solid electrolyte to the balls to the acetonitrile or absolute ethyl alcohol is (1), (0.8-1.5): (0.8-1.2), the ball milling rotating speed is 100 and 1000rpm, and the ball milling time is 0.5-20 h;
dissolving the ball-milled electrolyte powder in an organic solvent to obtain an electrolyte solution, wherein the mass ratio of the organic solvent to the electrolyte powder is (5-15):1, and the organic solvent is selected from one or more of acetonitrile, N-methyl amide, acetone, toluene, tetrahydrofuran, butyl butyrate, N-methyl pyrrolidone, N-heptane and ethanol;
preparing an electrode plate: and soaking the electrode material pole piece in the electrode material pole piece preparation step in the electrolyte solution preparation step for 0.5-10h, heating and drying at 80-200 ℃ for 0.5-10h under a vacuum condition, and tabletting to obtain the electrode pole piece.
In the process, in the preparation process of the electrode material pole piece, the electrode material is a positive electrode material or a negative electrode material, and the positive electrode material is selected from lithium cobaltate Li1+zCo1-nAnO2Ternary material Li1+zNixCoyM1-x-y-nAnO2Lithium-rich manganese mLi2MnO3·(1-m)Li1+zNixCoyMn1-x-y-n AnO2Ni-Mn spinel Li1+zNi0 .5-hMn1 .5-nAnO4Lithium iron manganese phosphate Li1+zFexMn1-x- nAnPO4Lithium manganate Li1+zMn2-nAnO4Lithium iron phosphate Li1+zFe1-nAnPO4Wherein, z is more than or equal to 0 and less than 0.1, n is more than or equal to 0 and less than 0.1, x is more than 0 and less than 1, y is more than 0 and less than 1, x + y + n is more than 0 and less than 1, M is more than 0 and less than 1, h + l is equal to n, M is Mn or Al, A is at least one element of Ti, Mg, Al, Zr, Nb, Ba, La, V, W, Ag and Sn;
the negative electrode material is selected from one or more of artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads, metallic lithium, Li-C compounds, lithium alloys, transition metal oxides and lithium titanate.
The conductive agent is selected from one or more of carbon nano tube, carbon black, graphene and Ketjen black;
the binder is selected from one or more of polyvinylidene fluoride, polyvinyl alcohol, styrene butadiene rubber, sodium carboxymethylcellulose, nitrile butadiene rubber and silica gel;
the dispersing agent is selected from one or more of N-methyl pyrrolidone, water, toluene or xylene;
the pore-forming agent is one or more of oxalic acid, citric acid or benzoic acid;
the current collector is copper foil, aluminum foil, foamed nickel or other materials which can bear materials and have good conductivity.
In the preparation process of the electrolyte solution, the solid electrolyte is a solid polymer electrolyte or an inorganic solid electrolyte, the inorganic solid electrolyte comprises one or two of an oxide type solid electrolyte and a sulfide type electrolyte, the oxide type solid electrolyte is selected from garnet type solid electrolyte material, NASICON type solid electrolyte material, LISICON solid electrolyte material, perovskite type solid electrolyte material and one of the derivative materials thereof, wherein the derivative material of the oxide type solid electrolyte comprises one or a mixture of more of garnet type solid electrolyte material, NASICON type solid electrolyte material, LISICON solid electrolyte material and perovskite type solid electrolyte material, and the mixture is obtained by doping or coating2S，SiS2，P2S5And Li4Mixing substances such as SiO4 and the like, ball-milling for 2-10 h at the rotation speed of 100-1000rpm, and then calcining at high temperature to obtain the LISICON type electrolyte;
the sulfide-type solid electrolyte is crystalline or amorphous Li2S-P2S5Crystalline form of Li4MS4Crystalline form of Li10NP2S12Microcrystalline Li2S-P2S5-one or more of LiX and derived materials thereof; wherein M is selected from one or more of Si, Ge and Sn, N is selected from one or more of Si, Ge and Sn, X is selected from one or more of Cl, Br and I, 0 < X < 1, and the derivative material of the sulfide type solid electrolyte comprises binary sulfide Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3And ternary sulfide Li2S-MeS2-P2S5Wherein Me is selected from one of Si, Ge, Sn and Al, although the present invention discloses the above-mentioned several oxidation-type solid electrolytes, it is not limited thereto.
The polymer electrolyte comprises a polymer matrix and a lithium saltThe polymer matrix is one or more selected from polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylidene chloride and single ion polymer electrolyte, and the lithium salt is LiClO4、LiAsF4、LiPF6、LiBF4One or more of (a). The preparation method of the solid polymer is a conventional method, i.e. lithium salt is dissolved or mixed in a polymer matrix, the matrix is used as a solid solvent, and then the solid polymer is prepared by a solvent evaporation method, which is not described in detail.
Example 1
A preparation method of an electrode plate comprises the following steps:
s1, preparing an electrode material pole piece, namely stirring 95g of lithium cobaltate material, 2.0g of conductive agent carbon black, 2.0g of adhesive polyvinylidene fluoride, 90g of dispersing agent N-methyl pyrrolidone and 10g of pore-forming agent oxalic acid to prepare slurry with the solid content of 55%, and then coating the slurry on the surface of a current collector aluminum foil with the coating amount of 30 mg/cm2Drying at 115 ℃ for 1h to obtain an electrode material pole piece, wherein the electrode material is a positive electrode material LiCoO2；
S2, preparing an electrolyte solution: 40g of sulfide solid electrolyte was added to amorphous Li2S-P2S5Performing mechanical wet ball milling to obtain electrolyte powder, dissolving the ball-milled electrolyte powder in an organic solvent-absolute ethyl alcohol to obtain an electrolyte solution, and uniformly stirring by magnetic force to obtain the electrolyte solution, wherein the mass ratio of the organic solvent absolute ethyl alcohol to the electrolyte powder is 10:1, the wet ball milling medium is absolute ethyl alcohol, the mass ratio of the solid electrolyte, the ball and the medium absolute ethyl alcohol is 1: 1.5: 1.2, the ball milling speed is 500rpm, and the ball milling time is 10 hours;
s3, preparing an electrode plate: and (3) soaking the electrode material pole piece prepared in the step (S1) in the electrolyte solution prepared in the step (S2) for 5 hours, drying for 5 hours at 105 ℃ in an inert gas environment, volatilizing the solvent, and heating and drying for 1 hour at 180 ℃ under a vacuum condition to prepare the positive electrode pole piece.
Example 2
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that,
s1, preparing an electrode material pole piece, namely preparing 90g of positive electrode material LiNi0.5Co0.2Mn0.3O2Stirring 1.0g of single-walled carbon nanotube serving as a conductive agent, 4.0g of polyvinylidene fluoride serving as a binder, 51.2g N-methyl pyrrolidone dispersant and 5g of pore-forming agent-citric acid to prepare slurry with the solid content of 66%, and coating the slurry on the surface of an aluminum foil serving as a current collector in an amount of 7mg/cm2Drying for 2 hours at the temperature of 105 ℃ in vacuum to obtain an electrode material pole piece;
s2, preparing an electrolyte solution: 50g of a NASICON type solid electrolyte Li Zr2（PO4）3Performing mechanical wet ball milling to obtain electrolyte powder, dissolving the ball-milled electrolyte powder in organic solvent ethanol to obtain electrolyte solution, and uniformly stirring to obtain the electrolyte solution, wherein the mass ratio of the organic solvent ethanol to the electrolyte powder is 5:1, the wet ball milling medium is absolute ethanol, the mass ratio of the solid electrolyte, the ball and the medium absolute ethanol is 1: 0.8: 0.8, the ball milling speed is 100rpm, and the ball milling time is 20 hours;
s3, preparing an electrode plate: and (3) soaking the electrode material pole piece prepared in the step (S1) in the electrolyte solution prepared in the step (S2) for 0.5h, drying the electrode material pole piece for 8h at 60 ℃ in an inert gas environment, volatilizing the solvent, and heating and drying the electrode material pole piece for 0.5h at 100 ℃ under a vacuum condition to prepare the positive electrode pole piece.
Example 3
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that,
s1, preparing an electrode material pole piece, namely preparing 96g of lithium manganate LiMn serving as a positive electrode material2O45.0g of conductive agent carbon black, 3.0g of adhesive carboxymethylcellulose sodium, 127g of dispersing agent (N-methyl pyrrolidone) and 20g of pore-forming agent benzoic acid are stirred to prepare slurry with the solid content of 49%, and then the slurry is coated on the surface of current collector foamed nickel, wherein the coating amount is 38mg/cm2Drying at 130 ℃ for 1.5 h to obtain the electrode material pole piece；
S2, preparing an electrolyte solution: 55g of a LISICON type solid electrolyte Li14Zr(SO4)4Performing mechanical wet ball milling to obtain electrolyte powder, wherein a wet ball milling medium adopts absolute ethyl alcohol, the mass ratio of a solid electrolyte to balls to the absolute ethyl alcohol is 1: 1.5: 1.2, the ball milling rotation speed is 1000rpm, the ball milling time is 0.5h, the ball-milled electrolyte powder is dissolved in an organic solvent tetrahydrofuran to obtain an electrolyte solution, and the electrolyte solution is uniformly stirred, wherein the mass ratio of the tetrahydrofuran to the electrolyte powder is 15: 1;
s3, preparing an electrode plate: and (3) soaking the electrode material pole piece prepared in the step (S1) in the electrolyte solution prepared in the step (S2) for 10 hours, drying the electrode material pole piece for 2 hours at 85 ℃ in an inert gas environment, and heating and drying the electrode material pole piece for 8 hours at 150 ℃ under a vacuum condition to prepare the positive electrode pole piece.
Example 4
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that,
in step S1, the addition amount of the conductive agent is 0.1g, the addition amount of the adhesive is 1.0g, and the addition amount of the dispersing agent is 135g, so that slurry with the solid content of 40% is prepared;
in step S3, when the electrode material sheet is immersed in the electrolyte solution and dried, it is dried by heating at 80 ℃ for 10 hours under vacuum.
Example 5
A preparation method of an electrode plate is carried out according to the method in the embodiment 4, and the difference is that in the step S3, when the electrode plate is soaked in an electrolyte solution and then dried, the electrode plate is heated and dried for 0.5h at the temperature of 200 ℃ under the vacuum condition.
Example 6
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S1 of preparing the electrode material electrode plate, the positive electrode material is lithium-manganese-0.5 Li-rich2MnO3•0.5LiMn0.5Ni0.5O2(ii) a The conductive agent is graphene, and the binder is styrene butadiene rubber.
Example 7
The preparation method of the electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S1 of preparing the electrode material electrode plate, the positive electrode material is spinel LiMn2O4；
The conductive agent is Keqin black, and the binder is nitrile rubber.
Example 8
The preparation method of the electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S1 of preparing the electrode material electrode plate, the positive electrode material is lithium manganese iron phosphate LiFe0.5Mn0.5PO4。
Example 9
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S1 of preparing the electrode plate made of the electrode material, the anode electrode material is lithium iron phosphate (LiFePO)4。
Example 10
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is artificial graphite which is a negative electrode material.
Example 11
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is natural graphite which is used as a negative electrode material.
Example 12
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is soft carbon which is a negative electrode material.
Example 13
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is hard carbon which is a negative electrode material.
Example 14
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is selected from a negative electrode material mesocarbon microbeads.
Example 15
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is selected from a negative electrode material of metal lithium.
Example 16
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is a negative electrode material Li-C compound.
Example 17
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material plate in the step S1, the electrode material is selected from a negative electrode material lithium alloy.
Example 18
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the preparation of the electrode material electrode plate in the step S1, the electrode material is a negative electrode material, namely transition metal oxide nickel oxide NiO.
Example 19
A method for preparing an electrode plate, which is performed according to the method in the embodiment 1, and is characterized in that in the step S1, in the preparation of the electrode material electrode plate, the electrode material is a negative electrode material lithium titanate.
Example 20
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that in the step S2 of preparing the electrolyte solution, the solid electrolyte is perovskite type solid electrolyte LLTO (Li)3xL2/3-xTiO3，x=0.12）。
Example 21
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that in the step S2 of preparing the electrolyte solution, the solid electrolyte adopts solid polymer electrolysisThe solid polymer electrolyte consists of a polymer matrix of polyethylene oxide and a lithium salt LiClO4Preparation to obtain PEO/LiClO4The solid polymer electrolyte is prepared by the following steps: 1.256g PEO (Mn = 5X 106) were mixed with 0.382g LiClO4Dissolving the solid polymer electrolyte in 26g of acetonitrile, magnetically stirring the solution at the constant temperature of 30 ℃ for 12h, casting the solution in a polytetrafluoroethylene mold, naturally volatilizing the solution to form a film, and drying the film in vacuum at the temperature of 60 ℃ for 72h to obtain the solid polymer electrolyte, and dissolving the obtained solid polymer electrolyte in an organic solvent-absolute ethyl alcohol according to the method in the embodiment 1 to obtain an electrolyte solution.
Example 22
A preparation method of an electrode plate is carried out according to the method in the example 1, except that in the step S1, the addition amount of a pore-forming agent is 5g in the preparation of the electrode material plate.
Example 23
A preparation method of an electrode plate is carried out according to the method in the example 1, except that in the step S1, the addition amount of a pore-forming agent is 20g in the preparation of the electrode material plate.
Example 24
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S2 of preparing the electrolyte solution, the rotation speed of wet ball milling is 100rpm, and the ball milling time is 20 h.
Example 25
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S2 of preparing the electrolyte solution, the rotation speed of wet ball milling is 1000rpm, and the ball milling time is 0.5 h.
Comparative example 1
A method for preparing an electrode tab, which is carried out in the same manner as in example 1, except that the electrolyte solution is prepared into a solid electrolyte membrane in step S2, and a battery is assembled.
Comparative example 2
The preparation method of the electrode plate is carried out according to the method in the embodiment 1, and the difference is that in the step S2, in the preparation of the electrolyte solution, the dry ball milling is adopted as the method for ball milling the solid electrolyte into the solid electrolyte powder.
Comparative example 3
A preparation method of an electrode plate is carried out according to the method in the embodiment 1, except that the addition amount of the pore-forming agent is 3 g.
Comparative example 4
A preparation method of an electrode sheet was carried out in the same manner as in example 1, except that the amount of the pore-forming agent added was 25 g.
Performance detection
1. Application of prepared electrode plate to liquid lithium battery
The positive electrode plate prepared in the above examples 1-9, 20-25 and comparative examples 1-4 is used in a solid-liquid mixed lithium battery, the solid-liquid mixed lithium battery is prepared according to a conventional process, the negative electrode plate is an artificial graphite negative electrode, and the electrolyte is 1.1M LiPF6The composite membrane is characterized in that a mixed system of 1.5wt% of VC (vinylene carbonate) and 1.5w% of PS (1-3 propane sultone) is selected as an EC/DMC/EMC (mass ratio of 1:1: 1) and an additive, wherein the EC is vinylene carbonate, the DMC is dimethyl carbonate, the EMC is ethyl methyl carbonate, and the membrane is a 10PP-PE-PP three-layer composite membrane. And (4) detecting the prepared liquid lithium battery according to the following detection items.
Similarly, the negative electrode plate prepared in the above examples 10 to 19 was used in a solid-liquid mixed lithium battery prepared by a conventional process, and the positive electrode plate was lithium cobaltate LiCoO2The electrolyte is 1M LiPF6EC/DMC (mass ratio of 1: 2) and mixed electrolyte using 1wt% of VC and 1wt% of FEC (fluoroethylene carbonate) as additives, wherein the diaphragm adopts a 10PP-PE-PP three-layer composite diaphragm. And (4) detecting the prepared liquid lithium battery according to the following detection items.
1. And (3) rate performance detection: at normal temperature, a charge and discharge tester is used for testing, the battery is charged, the voltage after charging is 4.2V, 0.2C, 0.5C, 1C, 2C and 3C multiplying power charge and discharge is adopted, the termination voltage is set to be 3V, the 0.5C capacity, 1C capacity retention ratio, 2C capacity retention ratio, 3C capacity retention ratio and the battery capacity (0.5C) are tested, and the test results are shown in the following table 1 and table 2 (battery capacity);
2. and (3) detecting the cycle performance: the cycle test is carried out by determining the 1C cycle retention rate @200 cycles at normal temperature (25 ℃) according to the national standard GB/T31484-2015, and the detection result is shown in the following table 2;
3. a charge-discharge tester is used for testing the first discharge specific capacity under the multiplying power of 0.1C and measuring the first coulombic efficiency of the lithium battery, and the detection results are shown in the following table 2;
4. internal resistance test experiment: the internal resistance of the invention adopts a German Zahner electrochemical workstation to carry out alternating current impedance test; the test system is a U-Buffer two-electrode system, the test frequency range is 0.01Hz-100KHz, the amplitude is 5mV, the internal resistance of the alternating current impedance is measured, and the detection result is shown in the following table 2.
TABLE 1 Rate Performance test results
Numbering 0.5C capacity 1C capacity retention rate 2C capacity retention rate 3C capacity retention ratio
Example 1 101.92% 100% 95.87% 90.98%
Example 2 102.32% 100% 95.05% 84.36%
Example 3 102.51% 100% 93.26% 83.52%
Example 4 102.15% 100% 95.12% 87.12%
Example 5 101.98% 100% 95.79% 88.06%
Example 6 102.36% 100% 91.54% 80.37%
Example 7 101.25% 100% 92.65% 79.78%
Example 8 101.64% 100% 92.08% 80.12%
Example 9 102.45% 100% 95.54% 85.78%
Example 10 103.81% 100% 93.73% 87.27%
Example 11 101.77% 100% 93.59% 86.23%
Example 12 102.02% 100% 92.56% 85.45%
Example 13 101.73% 100% 93.45% 90.32%
Example 14 102.21% 100% 94.62% 89.34%
Example 15 101.12% 100% 92.84% 80.12%
Example 16 101.65% 100% 91.02% 79.13%
Example 17 101.19% 100% 92.95% 81.46%
Example 18 101.05% 100% 91.89% 78.05%
Example 19 102.08% 100% 92.58% 82.05%
Example 20 102.28% 100% 92.35% 84.48%
Example 21 101.37% 100% 93.31% 83.26%
Example 22 100.89% 100% 92.47% 82.12%
Example 23 101.78% 100% 93.57% 84.97%
Example 24 101.15% 100% 93.17% 84.56%
Example 25 101.65% 100% 95.25% 84.11%
Comparative example 1 103.22% 100% 85.20% 69.61%
Comparative example 2 103.36% 100% 87.23% 75.13%
Comparative example 3 100.42% 100% 91.78% 77.21%
Comparative example 4 101.13% 100% 89.58% 72.97%
Table 2 other performance test results are as follows:
numbering Battery capacity (mAh) First coulombic efficiency (%) AC impedance internal resistance (m omega) 1C cycle retention @200 times (%)
Example 1 415.26 94.21% 91.5 97.7%
Example 2 405.34 86.71% 98.2 96.9%
Example 3 348.23 93.88% 105.6 86.1%
Example 4 400.17 92.23% 100.2 95.7%
Example 5 408.78 92.97% 92.1 96.9%
Example 6 645.22 86.67% 139.7 85.2%
Example 7 404.87 80.15% 145.8 82.8%
Example 8 358.24 92.45% 125.2 94.2%
Example 9 337.12 94.91% 112.5 97.2%
Example 10 413.51 93.27% 90.3 97.6%
Example 11 410.23 91.36% 93.8 92.7%
Example 12 398.25 90.57% 94.8 89.5%
Example 13 381.23 88.78% 98.7 90.4%
Example 14 402.12 92.45% 92.4 91.2%
Example 15 410.35 93.67% 118.9 89.3%
Example 16 407.45 93.45% 114.5 90.1%
Example 17 396.83 92.42% 109.8 90.2%
Example 18 385.56 90.78% 125.8 84.5%
Example 19 389.78 90.25% 105.6 93.1%
Example 20 414.26 93.06% 96.7 96.7%
Example 21 414.11 91.67% 110.9 95.2%
Example 22 356.78 86.57% 112.5 88.4%
Example 23 387.45 90.12% 102.5 92.4%
Example 24 382.58 90.46% 128.9 92.1%
Example 25 398.56 92.45% 102.5 95.5%
Comparative example 1 397.27 89.88% 138.1 75.1%
Comparative example 2 385.38 88.79% 136.2 81.7%
Comparative example 3 257.89 75.65% 168.5 77.2%
Comparative example 4 312.53 79.84% 149.8 81.2%
The above table shows that the 3C capacity retention rate of the electrode plate prepared by the preparation method provided by the invention is more than 90%, and the 1C cycle retention rate @200 times is more than 80% when the electrode plate is used in a lithium battery, and the electrode plate prepared by the preparation method provided by the invention has good cycle performance and rate capability.
It can be seen from the data in examples 10 to 19 that the negative electrode material is made of a carbon material, which is better than other materials, especially the artificial graphite has the best comprehensive electrochemical performance, the mesocarbon microbeads and hard carbon have better rate capability, and the cycle is relatively poor when the negative electrode material is made of lithium metal or metal oxide.
From the data of examples 22 and 23 and comparative examples 3 and 4, it can be seen that as the pore former addition amount increases, the battery capacity and the first coulombic efficiency increase and then decrease, and the cycle rate increases and then decreases, while the rate performance is optimal in example 1, when the pore former addition amount is 5-20g, the rate performance increases and then decreases slightly, and when the pore former addition amount is less than 5g, the battery rate performance is poor, and when the pore former addition amount is more than 20g, the rate performance is poor.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (10)

1. The preparation method of the electrode plate is characterized by comprising the following steps:
preparing an electrode material pole piece, namely stirring an electrode material, a conductive agent, an adhesive, a dispersing agent and a pore-forming agent to prepare slurry, coating the slurry on the surface of a current collector, and drying to obtain the electrode material pole piece;
electrolyte solution preparation: carrying out mechanical ball milling on the solid electrolyte to obtain electrolyte powder, and dissolving the electrolyte powder in an organic solvent to obtain an electrolyte solution;
preparing an electrode plate: and soaking the electrode material pole piece in an electrolyte solution, heating and drying, and tabletting to obtain the electrode pole piece.
2. The preparation method of the electrode plate according to claim 1, wherein in the step of preparing the electrode material plate, the preparation method of the slurry comprises the following steps in parts by weight: dissolving 90-96 parts of electrode material, 0.1-5.0 parts of conductive agent, 1.0-4.0 parts of adhesive and 5-20 parts of pore-forming agent in dispersing agent to prepare slurry with solid content of 40-70%.
3. The method for preparing an electrode plate according to claim 1, wherein in the step of preparing the electrode material plate, the electrode material is a positive electrode material or a negative electrode material, and the positive electrode material is selected from lithium cobaltate Li1+zCo1-nAnO2Ternary material Li1+zNixCoyM1-x-y-nAnO2Lithium-rich manganese mLi2MnO3·(1-m)Li1+zNixCoyMn1-x-y-n AnO2Ni-Mn spinel Li1+zNi0 .5-hMn1 .5-lAnO4Lithium iron manganese phosphate Li1+zFexMn1-x-nAnPO4Lithium manganate Li1+zMn2-nAnO4Lithium iron phosphate Li(1+z)Fe(1-n)AnPO4Wherein, z is more than or equal to 0 and less than 0.1, n is more than or equal to 0 and less than 0.1, x is more than 0 and less than 1, y is more than 0 and less than 1, x + y + n is more than 0 and less than 1, M is more than 0 and less than 1, h + l is equal to n, M is Mn or Al, A is at least one element of Ti, Mg, Al, Zr, Nb, Ba, La, V, W, Ag and Sn;
the negative electrode material is selected from one or more of artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads, metallic lithium, Li-C compounds, lithium alloys, transition metal oxides and lithium titanate.
4. The method for preparing the electrode plate according to claim 2, wherein in the step of preparing the electrode material, the conductive agent is one or more selected from carbon nanotubes, carbon black, graphene and ketjen black;
the binder is selected from one or more of polyvinylidene fluoride, polyvinyl alcohol, styrene butadiene rubber, sodium carboxymethylcellulose, nitrile butadiene rubber and silica gel;
the dispersing agent is selected from one or more of N-methyl pyrrolidone, water, toluene or xylene;
the pore-forming agent is one or more of oxalic acid, citric acid or benzoic acid.
5. The preparation method of the electrode plate as claimed in claim 1, wherein in the step of preparing the electrode material plate, the slurry is coated on the surface of the current collector, the drying temperature is 60-130 ℃, the drying time is 0.5-2h, and the coating amount is 1-100mg/cm2；
The current collector is selected from any one of copper foil, aluminum foil and foamed nickel.
6. The method for preparing the electrode plate according to claim 1, wherein in the step of preparing the electrolyte solution, the mass ratio of the organic solvent to the electrolyte powder is (5-15): 1;
the solid electrolyte is a polymer electrolyte or an inorganic solid electrolyte;
the polymer electrolyte is composed of a polymer matrix and lithium salt, the polymer body is selected from one or more of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylidene chloride and single-ion polymer electrolyte, and the lithium salt is LiClO4、LiAsF4、LiPF6、LiBF4One or more of;
the inorganic solid electrolyte comprises one or two of an oxide solid electrolyte and a sulfide solid electrolyte, wherein the oxide solid electrolyte is selected from one of a garnet solid electrolyte material, an NASICON solid electrolyte material, a LISICON solid electrolyte material, a perovskite solid electrolyte material and a derivative material thereof, and the derivative material of the oxide solid electrolyte comprises one or a mixture of more of the garnet solid electrolyte material, the NASICON solid electrolyte material, the LISICON solid electrolyte material and the perovskite solid electrolyte material, and is obtained by doping or coating;
the sulfide-type solid electrolyte is in a crystalline state orAmorphous Li2S-P2S5Crystalline form of Li4MS4Crystalline form of Li10NP2S12Microcrystalline Li2S-P2S5-one or more of LiX and derived materials thereof; wherein M is selected from one or more of Si, Ge and Sn, N is selected from one or more of Si, Ge and Sn, X is selected from one or more of Cl, Br and I, 0 < X < 1, and the derivative material of the sulfide type solid electrolyte comprises binary sulfide Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3And ternary sulfide Li2S-MeS2-P2S5The one or more than one of the above components are doped or coated, wherein Me is selected from one of Si, Ge, Sn and Al.
7. The preparation method of the electrode plate according to claim 1, wherein in the step of preparing the electrolyte solution, the mechanical ball milling is performed by wet mechanical ball milling, a medium of the wet ball milling is acetonitrile or absolute ethyl alcohol, and the mass ratio of the solid electrolyte, the ball and the acetonitrile or absolute ethyl alcohol is 1 (0.8-1.5): (0.8-1.2), the ball milling speed is 100 and 1000rpm, and the ball milling time is 0.5-20 h.
8. The method for preparing the electrode plate according to claim 1, wherein in the step of preparing the electrode plate, when the electrode material tabs are soaked in the electrolyte solution, the soaking time is 0.5-10h, the heating and drying are carried out under the vacuum condition, the heating temperature is 80-200 ℃, and the heating time is 0.5-10 h.
9. An electrode plate, characterized in that the electrode plate of the solid-state lithium ion battery is prepared by the preparation method of the electrode plate according to any one of claims 1 to 8.
10. The use of an electrode tab according to claim 9, wherein the electrode tab is used in any one of a conventional liquid lithium battery, a polymer lithium battery, a mixed solid-liquid electrolyte lithium battery, and a solid lithium battery.
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CN113308604A (en) * 2021-04-26 2021-08-27 湖南大学 Intrinsic safety processing method for edge metal in retired battery pole piece and application
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Application publication date: 20201229