CN116469601A - Conductor dispersion liquid, preparation method, positive electrode plate and solid-state battery - Google Patents

Conductor dispersion liquid, preparation method, positive electrode plate and solid-state battery Download PDF

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CN116469601A
CN116469601A CN202310423744.3A CN202310423744A CN116469601A CN 116469601 A CN116469601 A CN 116469601A CN 202310423744 A CN202310423744 A CN 202310423744A CN 116469601 A CN116469601 A CN 116469601A
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positive electrode
equal
conductor
dispersion liquid
inorganic electrolyte
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郭峰
谢茂玲
张果
赵江辉
魏文硕
乐超
涂玉祖
王国荣
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Zhejiang Chint Electrics Co Ltd
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Zhejiang Chint Electrics Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application discloses a conductor dispersion liquid and a preparation method thereof, an anode plate and a solid-state battery, and relates to the technical field of solid-state batteries, and the preparation method comprises the following steps: providing inorganic electrolyte particles and a nano carbon material, mixing and dispersing the inorganic electrolyte particles and the nano carbon material to obtain pre-dispersed powder; providing a dispersing agent and a solvent, and mixing the dispersing agent, the solvent and the pre-dispersed powder to obtain a conductor dispersion liquid. According to the preparation method, the nano carbon material and the inorganic electrolyte particles are mixed, so that the nano carbon material is adsorbed on the surfaces of the inorganic electrolyte particles to generate steric hindrance, the self structure of the inorganic electrolyte particle material cannot be damaged, and the conductor dispersion liquid with high dispersion uniformity, high solid content and high stability can be obtained.

Description

Conductor dispersion liquid, preparation method, positive electrode plate and solid-state battery
Technical Field
The application relates to the technical field of solid-state batteries, in particular to a conductor dispersion liquid, a preparation method, an anode plate and a solid-state battery.
Background
Energy density and safety are the focus of current lithium battery research, and solid-state batteries using metallic lithium anodes have potential advantages in terms of high energy density, high safety, recyclability, low cost, and the like, as compared with conventional liquid lithium ion batteries. The problem of ion and electron transport inside the positive electrode is one of the important research points for the preparation of solid-state batteries with high energy density and high safety.
The current strategy for improving the ionic and electronic conductivity of the solid anode is endless and mainly comprises the steps of adding ionic and electronic conductor materials, coating the surface of the anode material, nanocrystallizing the material and the like in a formula. In the strategy of adding ion and electron conductor materials in the formula, common ion conducting materials comprise inorganic electrolyte materials such as LIPON, LISICON, garnet, perovskite and the like, and common electron conducting materials comprise conductive materials such as carbon fibers, carbon nanotubes, graphene and the like or conductive polymer materials. The common adding method is to simply and mechanically mix the solid electrolyte material and the electron conductive additives such as conductive carbon, and the like, so that the problems of material agglomeration, poor interface contact, uneven material distribution and the like are easy to occur, the conductive uniformity and the electrochemical stability in the composite positive electrode are severely limited, and a continuous, uniform and effective electron/ion conductive network is difficult to construct. In addition, the polymer system with ion conduction and electron conduction is designed to construct an internal ion and electron transmission network, but the polymer system often has the problems of low lithium ion conductivity, poor flexibility, poor mechanical strength and the like at room temperature, and when the electronically conductive polymer with a large delocalized pi-bond rigid structure and the electronically conductive polymer with a flexible group with strong electronegativity are mixed, the problems of poor ion and electron conductivity and the like caused by mutual interference of entanglement of polymer chain segments can occur, so that the development of the mixed conductor with high ion conductivity, high electron conductivity, high mechanical strength, high chemical stability and electrochemical stability has a certain technical difficulty. In addition, there have been studied methods for preparing oxide or sulfide/metal composite conductive materials by a lithium simple substance reduction method or a chemical lithiation method using a reducing lithium-containing compound such as t-butyllithium, which are complicated in experimental operation and high in risk, and raw materials used have high chemical activity so that the preparation method thereof is unfavorable for mass process production.
Aiming at the problem of transportation of ions and electrons in the positive electrode of the solid-state battery, the series of coping strategies have certain defects. And the lattice distortion and the volume change of particles of the electrode material can damage a continuous ion and electron transmission network between the active substance, the electrolyte and the conductive agent in the solid-state battery circulation process, so that the ion and electron transport is further hindered, and the active material load in the existing composite electrode is lower, so that the energy density of the all-solid-state battery is lower.
Therefore, a simple method suitable for large-scale process production is needed to construct continuous, effective and uniformly distributed ion and electron networks in the composite positive electrode of the solid-state battery, improve the loading of active materials and the uniformity of material dispersion, improve interface contact and adapt to the volume change of electrode materials in the circulating process while ensuring the chemical and electrochemical stability of the composite positive electrode, and finally realize the preparation of the full-solid-state battery with high circulating stability and high energy density.
Disclosure of Invention
In view of the above, the present application provides a conductor dispersion liquid, a preparation method thereof, a positive electrode sheet and a solid-state battery, and aims to solve the problem of uneven distribution of the existing ion and electron conductive materials.
The embodiment of the application is realized in such a way that a preparation method of the conductor dispersion liquid comprises the following steps:
providing inorganic electrolyte particles and a nano carbon material, mixing and dispersing the inorganic electrolyte particles and the nano carbon material to obtain pre-dispersed powder;
providing a dispersing agent and a solvent, and mixing the dispersing agent, the solvent and the pre-dispersed powder to obtain a conductor dispersion liquid.
Optionally, in some embodiments of the present application, the mass ratio of the inorganic electrolyte particles to the nanocarbon material is (0.25 to 800): 1, a step of; and/or
In the conductor dispersion liquid, the solid content of the inorganic electrolyte particles is 5-80 wt%; and/or
In the conductor dispersion liquid, the solid content of the nano carbon material is 0.1-20wt%; and/or
In the conductor dispersion liquid, the mass fraction of the dispersing agent is 0.01-2 wt%.
Optionally, in some embodiments of the present application, the material of the inorganic electrolyte particles includes one or more of perovskite type material, NASICON type material, garnet type material, lithium phosphorus oxygen nitrogen type material; and/or
Average particle diameter D of the inorganic electrolyte particles 50 5-1000 nm; and/or
The nano carbon material comprises one or more of carbon black, acetylene black, carbon nano tubes, graphene, ketjen black and vapor phase growth carbon fibers; and/or
The structure of the nano carbon material comprises one or more of a punctiform structure, an amorphous structure, a sheet-shaped structure, a tubular structure, a linear structure and a spherical structure; and/or
The dispersing agent comprises one or more of a non-polymer dispersing agent and a polymer dispersing agent; and/or
The solvent comprises an aprotic polar solvent.
Optionally, in some embodiments of the present application, the perovskite-type material comprises Li a La b Ti c A d O e Wherein a is more than 0 and less than or equal to 0.5, b is more than 0 and less than or equal to 0.6,0.9, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.25,2 and e is less than or equal to 3, and A comprises one or more of Ba, sr and Al; and/or
The NASICON type material comprises Li f B g P h O 12 Wherein f is more than or equal to 1 and less than or equal to 3, g is more than or equal to 0 and less than or equal to 4, h is more than or equal to 1 and less than or equal to 3, and B comprises one or more than one of Al, zr, ti, ge, si; and/or
The garnet-type material comprises Li i La j Zr k C l O 12 Wherein i is more than 5 and less than or equal to 7, j is more than 2 and less than or equal to 3, k is more than 1 and less than or equal to 2, l is more than 0 and less than 1, and C comprises one or more than one of Al, nb, ca, W, ta; and/or
The lithium phosphorus oxygen nitrogen material comprises LiPON; and/or
The non-polymer dispersing agent comprises one or more of dodecyl maltoside, cetyl trimethyl ammonium bromide, bile acid salt and steroid zwitterionic surfactant; and/or
The polymer type dispersing agent comprises one or more of alkylphenol ethoxylates, wholly aromatic polyamide, semi-aromatic polyamide and polyvinylpyrrolidone; and/or
The aprotic polar solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, acetone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile and hexamethylphosphoric triamide.
Optionally, in some embodiments of the present application, the dispersing method is a first grinding of the mixed inorganic electrolyte particles and the nanocarbon material by a grinding medium; and/or
The dispersant, the solvent and the pre-dispersed powder are mixed and then further comprise: and carrying out second grinding on the mixed dispersing agent, solvent and pre-dispersed powder through a grinding medium.
Optionally, in some embodiments of the present application, the grinding media comprises one or more of zirconia beads, zirconium beads, glass beads; and/or
The average grain diameter of the grinding medium is 0.03-5 mm; and/or
The first grinding and the second grinding respectively and independently comprise one or more of high-energy ball mill grinding, mechanical stirrer grinding, vertical stirrer grinding and sand mill grinding.
Correspondingly, the embodiment of the application also provides a conductor dispersion liquid, which is prepared by the preparation method of the conductor dispersion liquid.
Correspondingly, the embodiment of the application also provides a positive electrode plate, which comprises a positive electrode material, a first nano carbon material, a binder and the conductor dispersion liquid prepared by the preparation method of the conductor dispersion liquid.
Optionally, in some embodiments of the present application, the positive electrode sheet comprises a carbon electronic conductor material comprising the first nanocarbon material and the nanocarbon material in the conductor dispersion;
in the positive electrode sheet, the mass ratio of the positive electrode material to the inorganic electrolyte particles to the carbon electron conductor material to the binder is (87-99.5): (0.1-10): (0.1-1.5): (0.3-1.5).
Optionally, in some embodiments of the present application, the positive electrode material includes one or more of lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese phosphate, lithium nickel manganese oxide, sulfur material, polymer-sulfur material; and/or
The binder comprises one or more of polyvinylidene fluoride, polyacrylonitrile, styrene-butadiene latex, polyimide, hydroxymethyl cellulose, polytetrafluoroethylene emulsion, polyacrylate, hydrogenated nitrile rubber and polyurethane.
Correspondingly, the embodiment of the application also provides a solid-state battery, which comprises a negative electrode plate, a solid-state electrolyte and the positive electrode plate.
According to the preparation method of the conductor dispersion liquid, the inorganic electrolyte particles and the nano carbon material are mixed to prepare pre-dispersion powder which is uniformly dispersed, then the pre-dispersion powder is mixed with the dispersing agent and the solvent to prepare the conductor dispersion liquid, the nano carbon material and the inorganic electrolyte particles are mixed, the nano carbon material is adsorbed on the surfaces of the inorganic electrolyte particles to generate steric hindrance, the self structure of the inorganic electrolyte particles is not damaged, and the conductor dispersion liquid with high dispersion uniformity, high solid content and high stability can be obtained; the inorganic electrolyte particles selected by the application have the characteristics of intrinsic high ion conductivity and mechanical property, the nano carbon material has the characteristics of intrinsic high electron conductivity, the particle sizes of the inorganic electrolyte particles and the nano carbon material are both in the nano size range, the inorganic electrolyte particles have high chemical compatibility and chemical stability, and the preparation of the high-load positive electrode can be realized under the condition of small use. The preparation method of the conductor dispersion liquid is simple and convenient to operate, and the prepared conductor dispersion liquid has good chemical compatibility and chemical stability, and can realize large-scale preparation, storage and use
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method of preparing a conductor dispersion provided in an embodiment of the present application;
FIG. 2 is a graph of the microtopography provided by the positive electrode sheet of example 1 of the battery of the present application;
FIG. 3 is a mapping spectrum of carbon element provided by the positive electrode sheet of example 1 of the battery of the present application;
FIG. 4 is a mapping spectrum of titanium element provided by the positive electrode sheet of example 1 of the battery of the present application;
fig. 5 is a comparative graph of the charge-discharge cycle performance of the button cell provided in example 1 and comparative example 1 of the battery of the present application;
fig. 6 is a charge-discharge graph of the second and third turns of battery example 1 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower positions of the device in actual use or operation, and specifically the orientation of the drawing figures; while "inner" and "outer" are for the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction.
In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.
In this application, "at least one" means one or more, and "a plurality" means two or more. "one or more," "at least one of," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The technical scheme of the application is as follows:
in a first aspect, referring to fig. 1, an embodiment of the present application provides a method for preparing a conductor dispersion, including the following steps:
step S11: providing inorganic electrolyte particles and a nano carbon material, mixing and dispersing the inorganic electrolyte particles and the nano carbon material to obtain pre-dispersed powder;
step S12: providing a dispersing agent and a solvent, and mixing the dispersing agent, the solvent and the pre-dispersed powder to obtain a conductor dispersion liquid.
According to the preparation method of the conductor dispersion liquid, the inorganic electrolyte particles and the nano carbon material are mixed to prepare the pre-dispersion powder which is uniformly dispersed, and then the pre-dispersion powder is mixed with the dispersing agent and the solvent to prepare the conductor dispersion liquid, on one hand, the steric hindrance generated by the adsorption of the nano carbon material on the surfaces of the inorganic electrolyte particles does not damage the self structure of the inorganic electrolyte particle materials, and the conductor dispersion liquid with high dispersion uniformity, high solid content and high stability can be obtained; on the other hand, the selected inorganic electrolyte particles have intrinsic high ion conductivity and mechanical property, the nano carbon material has intrinsic high electron conductivity, the particle diameters of the inorganic electrolyte particles and the nano carbon material are in the nano size range, the inorganic electrolyte particles have high chemical compatibility and chemical stability, and the preparation of the high-load positive electrode can be realized under the condition of small use. The preparation method of the conductor dispersion liquid is simple and convenient to operate, and the prepared conductor dispersion liquid is good in chemical compatibility and chemical stability and can be prepared, stored and used in a large scale.
In the step S11:
in some embodiments, the inorganic electrolyte material comprises an oxide solid state electrolyte. The oxide solid electrolyte comprises one or more of crystalline solid electrolyte and glassy solid electrolyte.
In some embodiments, the material of the crystalline solid state electrolyte comprises one or more of perovskite type material, NASICON type material, garnet type material.
The perovskite type material comprises Li a La b Ti c A d O e Wherein a is more than 0 and less than or equal to 0.5, b is more than 0 and less than 0.6,0.9, c is more than or equal to 1, d is more than or equal to 0 and less than or equal to 0.25,2 and e is more than or equal to 3, and A comprises Ba, sr and Al.
Illustratively, the perovskite-type material includes Li 0.5 La 0.5 TiO 3 、Li 0.29 La 0.57 TiO 3 、Li 0.30 La 0.57 TiO 3 、Li 0.33 La 0.56 TiO 3 、Li 0.34 La 0.51 TiO 2.94 、Li 0.30 La 0.567 TiO 3 、Li 0.36 Sr 0.04 La 0.523 TiO 3 、Li 0.5 La 0.5 TiO 3 、Li 0.33 Ba 0.25 La 0.39 TiO 3 (Li) 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01 O 3 One or more of them.
The NASICON type material comprises Li f B g P h O 12 Wherein f is more than or equal to 1 and less than or equal to 3, g is more than or equal to 0 and less than or equal to 4, h is more than or equal to 1 and less than or equal to 3, and B comprises one or more than one of Al, zr, ti, ge, si.
Illustratively, the NASICON-type material includes LiZr 2 (PO 4 ) 3 ，LiTi 2 (PO 4 ) 3 And LiGe 2 (PO 4 ) 3 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 3 Zr 2 Si 2 PO 12 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 、Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 And Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 One or more of them.
The garnet-type material comprises Li i La j Zr k C l O 12 Wherein i is more than 5 and less than or equal to 7, j is more than 2 and less than or equal to 3, k is more than 1 and less than or equal to 2, l is more than 0 and less than 1, and C comprises one or more than one of Al, nb, ca, W, ta.
Illustratively, the garnet-type material comprises Li 7 La 3 Zr 2 O 12 、Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 、Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 、Li 6.375 La 3 Zr 1.375 Nb 0.625 O 12 、Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 、Li 5.9 Al 0.2 La 3 Zr 1.75 W 0.25 O 12 、Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 、Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 Li (lithium ion battery) 6.4 La 3 Zr 1.4 Ta 0.6 O 12 One or more of them.
In some embodiments, the material of the glassy solid electrolyte comprises a lithium phosphorus oxygen nitrogen based material comprising LiPON.
In other embodiments, the material of the inorganic electrolyte particles may further include one or more of a sulfide solid state electrolyte, a borohydride solid state electrolyte.
In some embodiments, the inorganic electrolyte particles have an average particle size D 50 For example, the wavelength range is from 5 to 1000nm, and may be from 10 to 700nm, from 20 to 600nm, from 50 to 500nm, from 100 to 400nm, from 200 to 300nm, etc. The inorganic electrolyte particles are nano-scale in the particle size range, and have the characteristics of small particle size, good toughness, large specific surface area and the like, and have good interface contact when being compounded with the electronic conductive material.
In some embodiments, the nanocarbon material comprises one or more of carbon black, acetylene black, carbon nanotubes, graphene, ketjen black, vapor grown carbon fibers.
In some embodiments, the structure of the nanocarbon material comprises one or more of a dot-like structure, an amorphous structure, a sheet-like structure, a tubular structure, a wire-like structure, and a spherical structure.
In some embodiments, the mass ratio of the inorganic electrolyte particles to the nanocarbon material is (0.25 to 800): 1, for example, (1 to 700): 1, (10-650): 1, (100-600): 1, (200-500): 1, (250-450): 1, (300 to 400): 1, etc. The two powders can be effectively dispersed and form stable slurry within the ratio range.
In some embodiments, the dispersing method is a first grinding of the mixed inorganic electrolyte particles and the nanocarbon material by a grinding medium.
In some embodiments, the first milled milling media comprises one or more of zirconia beads, zirconium beads, glass beads.
The average particle diameter of the grinding medium is 0.03 to 5mm, and may be, for example, 0.05 to 4.5mm,0.1 to 4mm,0.5 to 3.5mm,1 to 3mm,1.2 to 2mm, etc. Within the particle size range, the abrasive mixing of the inorganic electrolyte particles and the nanocarbon material may be promoted.
In some embodiments, the first grinding comprises one or more of high energy ball mill grinding, mechanical agitator grinding, vertical agitator grinding, sand mill grinding.
The ball milling speed of the high-energy ball mill is 50-1000 r/min, for example, 100-900 r/min, 200-800 r/min, 300-700 r/min, 400-600 r/min, 500-550 r/min and the like; the ball milling time is 0.5 to 10 hours, for example, 1 to 9 hours, 2 to 8 hours, 3 to 7 hours, 4 to 6 hours, 5 to 5.5 hours, etc. Mixing of the inorganic electrolyte particles and the nanocarbon material may be promoted within the rate and time ranges of the ball milling.
The stirring speed of the mechanical stirrer is 100-5000 r/min, for example, 200-4500 r/min, 500-4000 r/min, 800-3500 r/min, 1000-3000 r/min, 1500-2000 r/min and the like; the stirring time is 0.5 to 24 hours, for example, 0.6 to 4.8 hours, 0.8 to 4.5 hours, 1 to 4 hours, 1.5 to 3.5 hours, 2 to 3 hours, and the like. Mixing of the inorganic electrolyte particles and the nanocarbon material may be promoted within the rate and time range of the stirring.
The stirring linear speed of the vertical stirrer is 1-30 m/s, for example, 2-25 m/s, 5-20 m/s, 8-18 m/s, 10-16 m/s, 12-15 m/s and the like; the stirring time is 0.5 to 24 hours, and may be, for example, 1 to 20 hours, 2 to 18 hours, 5 to 15 hours, 8 to 12 hours, 10 to 11 hours, or the like. Mixing of the inorganic electrolyte particles and the nanocarbon material may be promoted within the linear velocity and time range of the stirring.
The linear speed of the sand mill is 1-30 m/s, for example, 2-28 m/s, 5-25 m/s, 8-20 m/s, 10-18 m/s, 12-15 m/s, etc.; the sanding time is 0.5 to 24 hours, for example, 1 to 22 hours, 2 to 20 hours, 5 to 18 hours, 8 to 15 hours, 10 to 12 hours, etc. Mixing of the inorganic electrolyte particles and the nanocarbon material can be promoted within the linear velocity and time range of the sanding.
In the step S12:
in some embodiments, the dispersant comprises one or more of a non-polymeric dispersant and a polymeric dispersant. The dispersing agent can effectively disperse the pre-dispersed powder and prevent the pre-dispersed powder from re-agglomerating in the dispersion liquid.
The non-polymer dispersing agent comprises one or more of dodecyl maltoside, cetyl trimethyl ammonium bromide, bile acid salt and steroid zwitterionic surfactant.
The polymer type dispersing agent comprises one or more of alkylphenol ethoxylates, wholly aromatic polyamide, semi-aromatic polyamide and polyvinylpyrrolidone.
In some embodiments, the solvent comprises an aprotic polar solvent.
The aprotic polar solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, acetone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile and hexamethylphosphoric triamide.
In some embodiments, the dispersing agent, the solvent, and the pre-dispersed powder, after mixing, further comprise: and carrying out second grinding on the mixed dispersing agent, solvent and pre-dispersed powder through a grinding medium.
In some embodiments, the second milled milling media comprises one or more of zirconia beads, zirconium beads, glass beads.
The average particle diameter of the grinding medium is 0.03 to 5mm, and may be, for example, 0.1 to 4.5mm,0.5 to 4mm,0.8 to 3.5mm,1 to 3mm,2 to 2.5mm, or the like. Within the particle size range, the abrasive mixing of the pre-dispersed powder, the dispersant, and the solvent may be facilitated.
In some embodiments, the second grinding comprises one or more of high energy ball mill grinding, mechanical agitator grinding, vertical agitator grinding, sand mill grinding.
The ball milling speed of the high-energy ball mill is 50-1000 r/min, for example, 100-900 r/min, 200-800 r/min, 300-700 r/min, 400-600 r/min, 500-550 r/min and the like; the ball milling time is 0.5 to 12 hours, for example, 0.8 to 10 hours, 1 to 8 hours, 2 to 7 hours, 3 to 6 hours, 4 to 5 hours, etc. Sufficient mixing of the dispersant, the solvent and the pre-dispersion powder may be promoted over the rate and time of the ball milling.
The stirring speed of the mechanical stirrer is 100-5000 r/min, for example, 200-4500 r/min, 500-4000 r/min, 800-1800 r/min, 1000-3500 r/min, 1200-3000 r/min and the like; the stirring time is 0.5 to 24 hours, and may be, for example, 0.8 to 20 hours, 1 to 18 hours, 2 to 16 hours, 5 to 14 hours, 8 to 12 hours, etc. Sufficient mixing of the dispersant, the solvent and the pre-dispersion powder may be promoted over the rate and time of the agitation.
The stirring linear speed of the vertical stirrer is 1-30 m/s, for example, 2-28 m/s, 5-25 m/s, 8-20 m/s, 10-18 m/s, 12-15 m/s and the like; the stirring time is 0.5 to 24 hours, and may be, for example, 1 to 22 hours, 2 to 20 hours, 5 to 18 hours, 8 to 16 hours, 10 to 15 hours, or the like. Sufficient mixing of the dispersant, the solvent and the pre-dispersion powder may be promoted over the linear speed and time of the agitation.
The linear speed of the sand mill is 1-30 m/s, for example, 2-28 m/s, 5-25 m/s, 8-20 m/s, 10-18 m/s, 12-15 m/s, etc.; the stirring time is 0.5 to 24 hours, and may be, for example, 1 to 22 hours, 2 to 20 hours, 5 to 18 hours, 8 to 16 hours, 10 to 15 hours, or the like. Sufficient mixing of the dispersant, the solvent and the pre-dispersion powder can be promoted over the linear speed and time of the sanding.
In some embodiments, the solid content of the inorganic electrolyte particles in the conductor dispersion is 5wt% to 80wt%, for example, may be 10wt% to 75wt%,15wt% to 70wt%,20wt% to 60wt%,30wt% to 50wt%,40wt% to 45wt%, or the like. It is understood that the solid content of the inorganic electrolyte particles is the mass fraction content of the inorganic electrolyte particles in the conductor dispersion. Within the solid content range, the inorganic electrolyte can be uniformly dispersed in the dispersion liquid, and no secondary agglomeration and interaction with the carbon material occur.
In some embodiments, the solid content of the nanocarbon material in the conductor dispersion is 0.1wt% to 20wt%, for example, may be 0.5wt% to 19wt%,1wt% to 18wt%,2wt% to 17wt%,5wt% to 16wt%,8wt% to 15wt%,10wt% to 12wt%, or the like. It is understood that the solid content of the nanocarbon material is the mass fraction content of the nanocarbon material in the conductor dispersion. In the solid content range, the nano carbon material can be uniformly dispersed in the dispersion liquid, and the conditions of secondary agglomeration and interaction with the inorganic electrolyte are avoided.
In some embodiments, the mass fraction of the dispersant in the conductor dispersion is 0.1wt% to 2wt%, for example, may be 0.2wt% to 1.9wt%,0.5wt% to 1.8wt%,0.8wt% to 1.7wt%,1wt% to 1.6wt%,1.2wt% to 1.5wt%, and the like. In the mass fraction range, the dispersing agent can effectively disperse the two materials and prevent the materials from re-agglomerating in the dispersion liquid for the second time. In addition, the addition of the proportion does not affect the electrochemical performance of the later stage.
In a second aspect, the present embodiments also provide a conductor dispersion prepared by the method of preparing a conductor dispersion described above.
The conductor dispersion liquid is prepared by mixing inorganic electrolyte particles with a nano carbon material, then mixing the mixture with a dispersing agent and a solvent, wherein the conductor dispersion liquid has high dispersion uniformity, high solid content and high stability; the inorganic electrolyte particles have high intrinsic ion conductivity and mechanical property, the nano carbon material has high intrinsic electron conductivity, the particle diameters of the inorganic electrolyte particles and the nano carbon material are in the nano size range, the inorganic electrolyte particles have high chemical compatibility and chemical stability, and the preparation of the high-load anode can be realized under the condition of small use.
In a third aspect, embodiments of the present application further provide a positive electrode sheet, including a positive electrode material, the first nanocarbon material, a binder, and the conductor dispersion liquid prepared by the method for preparing a conductor dispersion liquid described above, or the conductor dispersion liquid described above, where the conductor dispersion liquid contains inorganic electrolyte particles and a nanocarbon material.
In some embodiments, the first nanocarbon material comprises one or more of carbon black, acetylene black, carbon nanotubes, graphene, ketjen black, vapor grown carbon fibers.
In some embodiments, the positive electrode material comprises one or more of lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese phosphate, lithium nickel manganese oxide, sulfur material, polymer-sulfur material.
In some embodiments, the binder comprises one or more of polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), styrene-butadiene latex (SBR), polyimide (PI), hydroxymethyl cellulose (CMC), polytetrafluoroethylene emulsion (PTFE), polyacrylate (PAA), hydrogenated nitrile rubber, polyurethanes.
In some embodiments, the preparation method of the positive electrode sheet comprises the following steps:
and providing positive electrode slurry, wherein the positive electrode slurry comprises a positive electrode material, a binder, a first solvent, a first nano carbon material and the conductor dispersion liquid, and drying the positive electrode slurry to obtain a positive electrode plate.
In some embodiments, the method of preparing the positive electrode slurry includes: providing a positive electrode material, a binder, a first solvent, a first nano carbon material and the conductor dispersion liquid, mixing, and performing ball milling treatment to obtain positive electrode slurry.
The ball milling treatment speed is 50-1000 r/min, for example, 100-900 r/min, 200-800 r/min, 300-700 r/min, 400-600 r/min, 500-550 r/min and the like; the time of the ball milling treatment is 1 to 24 hours, for example, 2 to 22 hours, 5 to 20 hours, 8 to 18 hours, 10 to 15 hours, and the like. Sufficient mixing of the positive electrode material, the binder, the first solvent, and the conductor dispersion may be promoted within the rate and time range of the ball milling treatment.
In some embodiments, the positive electrode sheet comprises a carbon electronic conductor material comprising the first nanocarbon material and the nanocarbon material in the conductor dispersion.
In some embodiments, in the positive electrode sheet, the mass ratio of the positive electrode material, the inorganic electrolyte particles, the carbon electronic conductor material, and the binder is (87 to 99.5): (0.1-10): (0.1-1.5): (0.3 to 1.5), for example, (90 to 95): (0.1-10): (0.1-1.5): (0.3-1.5), (87-99.5): (2-8): (0.1-1.5): (0.3-1.5), (87-99.5): (0.1-10): (0.5-1): (0.3-1.5), (87-99.5): (0.1-10): (0.1-1.5): (0.5-1). Within the mass ratio range, the materials can ensure that the positive electrode active material exerts intrinsic performance in a battery system.
In other embodiments, the method of preparing the positive electrode slurry includes: providing a positive electrode material and a binder, and carrying out premixing stirring; adding a first solvent for kneading and stirring; adding conductor dispersion liquid and a first nano carbon material to mix and stir; and then adding the first solvent for dilution stirring, defoaming stirring and obtaining the anode slurry.
The speed of the premixed stirring is 3 to 25rpm, for example, 4 to 24rpm,5 to 22rpm,6 to 21rpm,8 to 20rpm,10 to 15rpm, etc.; the time of the premixing and stirring is 10 to 20 minutes, for example, 11 to 19 minutes, 12 to 18 minutes, 13 to 16 minutes, 14 to 17 minutes, and the like. Sufficient mixing of the positive electrode material and the binder may be promoted over the rate and time of the premix agitation.
The kneading and stirring rate may be 1000 to 2000rpm, for example, 1100 to 1900rpm,1200 to 1800rpm,1300 to 1700rpm,1500 to 1600rpm, etc.; the kneading and stirring time is 20 to 40 minutes, and may be, for example, 21 to 38 minutes, 22 to 35 minutes, 23 to 33 minutes, 25 to 32 minutes, 28 to 30 minutes, and the like. Sufficient mixing of the positive electrode material, the binder, and the first solvent can be promoted within the rate and time range of the kneading agitation.
The speed of the mixing and stirring is 1000-2000 rpm, for example, 1100-1900 rpm, 1200-1800 rpm, 1300-1700 rpm, 1500-1600 rpm and the like; the mixing and stirring time is 30 to 60 minutes, for example, 32 to 58 minutes, 35 to 55 minutes, 38 to 52 minutes, 40 to 50 minutes, 42 to 46 minutes, and the like. Sufficient mixing of the positive electrode material, the binder, the first solvent, and the conductor dispersion may be promoted within the rate and time range of the mixing agitation.
The dilution stirring speed is 1500-2000 rpm, for example 1550-1950 rpm, 1600-1900 rpm, 1650-1850 rpm, 1700-1800 rpm, 1750-1780 rpm, etc.; the time for the dilution and stirring is 20 to 30 minutes, and may be, for example, 21 to 29 minutes, 22 to 28 minutes, 23 to 26 minutes, 24 to 27 minutes, and the like. In the speed and time range of the dilution and stirring, the positive electrode slurry can reach proper viscosity, and the subsequent preparation of the positive electrode plate is convenient.
The viscosity of the diluted and stirred system may be 4000 to 800map.S, for example 4200 to 7800map.S,4500 to 7500map.S,4800 to 700 map.S,5000 to 6500map.S,5500 to 600 map.S, etc., and it is possible to facilitate the application and drying of the positive electrode slurry.
The defoaming stirring speed is 50-100 rpm, for example, 55-95 rpm, 60-90 rpm, 65-85 rpm, 70-80 rpm, 72-78 rpm and the like; the defoaming and stirring time is 0.5 to 120min, for example, 1 to 100min,10 to 90min,20 to 80min,30 to 70min,40 to 60min and the like. And in the speed and time range of defoaming and stirring, the positive electrode slurry can be defoamed, so that the preparation of the positive electrode plate is facilitated.
In some embodiments, the positive electrode sheet comprises a carbon electronic conductor material comprising the first nanocarbon material and the nanocarbon material in the conductor dispersion.
In some embodiments, in the positive electrode sheet, the mass ratio of the positive electrode material, the inorganic electrolyte particles, the carbon electronic conductor material, and the binder is (87 to 99.5): (0.1-10): (0.1-1.5): (0.3 to 1.5), for example, (90 to 95): (0.1-10): (0.1-1.5): (0.3-1.5), (87-99.5): (2-8): (0.1-1.5): (0.3-1.5), (87-99.5): (0.1-10): (0.5-1): (0.3-1.5), (87-99.5): (0.1-10): (0.1-1.5): (0.5-1). Within the mass ratio range, the materials can ensure that the positive electrode active material exerts intrinsic performance in a battery system.
In some embodiments, the first solvent comprises N-methylpyrrolidone.
In some embodiments, the drying includes baking and drying.
The baking temperature is 35-120 ℃, for example, 40-110 ℃, 45-100 ℃, 50-90 ℃, 60-80 ℃, 70-75 ℃ and the like; the baking time is 1 to 48 hours, for example, 5 to 45 hours, 8 to 40 hours, 10 to 35 hours, 20 to 30 hours, etc. In the baking temperature and time range, the solvent of the positive electrode plate can be primarily dried, the temperature is mild, and the usability of the positive electrode plate is not affected.
The drying includes vacuum drying, wherein the temperature of the vacuum drying is 100-120 ℃, for example, 102-119 ℃, 105-118 ℃, 106-116 ℃, 108-115 ℃, 110-112 ℃ and the like; the vacuum drying time is 2 to 3 hours, for example, 2.1 to 2.9 hours, 2.2 to 2.8 hours, 2.3 to 2.7 hours, 2.4 to 2.6 hours and the like; the vacuum degree of the vacuum drying is 0.1 to 133Pa, and may be, for example, 5 to 130Pa,20 to 100Pa,30 to 90Pa,40 to 80Pa,50 to 60Pa, or the like. And in the vacuum drying temperature, time and vacuum degree range, the solvent of the positive electrode plate can be effectively removed, and the conductivity of the positive electrode plate is improved.
The positive electrode plate provided by the embodiment of the application comprises a positive electrode material, a binder and the conductor dispersion liquid, wherein in the conductor dispersion liquid, inorganic electrolyte particles and nano carbon materials are prepared by mixing, so that the conductor dispersion liquid has high dispersion uniformity, high solid content and high stability, the selected inorganic electrolyte particles have intrinsic high ion conductivity and mechanical property, the nano carbon materials have intrinsic high electron conductivity, the particle sizes of the nano carbon materials are in a nano size range, the nano carbon materials have high chemical compatibility and chemical stability, the preparation of a high-load positive electrode can be realized under the condition of small use, and a continuous, uniform and effective electron and ion transmission network is built in the positive electrode.
In a fourth aspect, embodiments of the present application also provide a solid-state battery including a negative electrode tab, a solid-state electrolyte, and a positive electrode tab as described above.
In some embodiments, the negative electrode tab comprises one or more of a metallic lithium negative electrode, a silicon-based negative electrode, a metallic lithium alloy negative electrode, a copper foil lithium-free negative electrode.
In some embodiments, the solid state electrolyte comprises one or more of a sulfide electrolyte, an oxide electrolyte, a halide electrolyte, a polymer electrolyte, or a composite electrolyte.
The sulfide electrolyte includes 75Li 2 S·25PZ 2 S、80LiS·20P 2 S 5 、75Li 2 S·21P 2 S 5 ·4P 2 O 5 、33(0.7B 2 S 3 ·0.3P 2 O 5 )·67Li 2 S、80Li 2 S·20P 2 S 5 、Li 7 P 3 S 11 、β-Li 3 PS 4 、Li 10 GeP 2 S 12 、Li 11 Si 2 PSi 2 、Li 10 GeP 2 S 11.7 O 0.3 、Li 2.25 Zn 0.375 PS 4 、Li 10 SiP 2 S 12 、Li 10 SnP 2 S 12 、Li 10 Si 0.3 Sn 0.7 P 2 S 12 、Li 10 Ge 0.6 Sn 0.4 P 2 S 11.2 Se 0.8 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、86.9Li 3 PS 4 ·13.1LiAlS 2 、Li 11 AIP 2 S 12 One or more of them.
The oxide electrolyte includes ZrO 2 Base electrolyte, ceO 2 Base electrolyte, bi 2 O 3 Base electrolyte, laGaO 3 Base electrolyte, sr 0.55 Na 0.45 SiO 2.755 、La 2 Mo 2 O 9 、La 1.9 Ba 0.1 Mo 1.85 W 0.15 O 8.95 One or more of them.
The halide electrolyte includes Li 2 MnCl 4 、LiYbF 4 、LiAlF 4 、Li 2 ZnCl 4 、Li 2 MgCl 4 、LiAICL 4 、Li 2 TiCl 4 、Li 1.52 Mn 1.24 Cl 4 、Li 2 CdCl 4 、Li 1. 9Cd 1.05 Cl 4 、Li 2 FeCl 4 、Li 4 PbI 6 、Li 2 PbI 4 、Li 2 MgBr 4 、Li 3 InCl 6 、Li 3 InBr 6 、Li 3 InBr 3 Cl 3 、LilnBr 4 、Li 3 YCl 6 、Li 6 FeCl 8 、Li 6 CoCl 8 、Li 6 VCl 8 、Li 3 YBr 6 One or more of them.
The polymer electrolyte comprises one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), polytrimethylene carbonate (PTMC), polyvinyl carbonate (PEC), polypropylene carbonate (PPC), polyethylene carbonate (PVC), polycaprolactone diol (PCL), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), carboxymethyl cellulose (CMC) and poly (1, 3-dioxolane).
The composite electrolyte comprises more than two electrolytes.
In some embodiments, the solid state battery comprises one of a button cell battery or a pouch cell battery.
In some embodiments, the method of making a button cell comprises: and cutting the positive electrode plate into a wafer, and assembling the wafer with the solid electrolyte and the negative electrode plate in an inert gas atmosphere to obtain the button cell.
In some embodiments, the method for preparing the soft pack battery comprises: and stacking the positive electrode plate, the solid electrolyte and the negative electrode plate, packaging and welding to obtain the soft-package battery.
The solid-state battery provided by the embodiment of the application contains the conductor dispersion liquid in the positive electrode plate, so that high dispersion uniformity of the ion conductive material and the electron conductive material in the positive electrode plate can be ensured, a continuous, uniform and effective electron and ion transmission network in the positive electrode is constructed, and the energy density and the service performance of the solid-state battery are improved.
The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.
Example 1
The present embodiment provides a conductor dispersion liquid including inorganic electrolyte particles Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 (LATP), carbon nanotubes and dispersant poly (lation)Vinylpyrrolidone, the preparation method thereof is as follows:
weigh 250gLi 1.3 Al 0.3 Ti 1.7 P 3 O 12 Mixing with 2.5g of carbon nano tubes, and then ball milling for 1h at the speed of 200r/min to obtain uniformly dispersed pre-dispersed powder;
101g of the pre-dispersed powder, 0.4g of dispersing agent polyvinylpyrrolidone and 99g of N-methyl pyrrolidone solvent are weighed, mixed with 66.7g of zirconia beads with the average particle size of 0.03mm, ball-milled for 3 hours at the speed of 300r/min by a high-energy ball mill, and the zirconia beads are filtered by a screen to obtain conductor dispersion.
In this example, the solid content of the inorganic electrolyte particulate material in the conductor dispersion was 50wt%, the solid content of the nanocarbon material was 0.5wt%, and the mass fraction of the dispersant was 0.2wt%.
Example 2
The present embodiment provides a conductor dispersion liquid including inorganic electrolyte particles Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), carbon nanotubes and a dispersing agent polyvinylpyrrolidone, and the preparation method is as follows:
weigh 200gLi 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Mixing with 1g of carbon nano tube, and ball milling for 1h at the speed of 200r/min to obtain uniformly dispersed pre-dispersed powder;
120.6g of the pre-dispersed powder, 0.6g of dispersing agent polyvinylpyrrolidone and 79.4g of N-methyl pyrrolidone solvent are weighed, mixed with 66.7g of zirconia beads with the average particle size of 0.03mm, ball-milled for 3 hours by a high-energy ball mill at the speed of 300r/min, and the zirconia beads are filtered by a screen to obtain conductor dispersion.
In this example, the solid content of the inorganic electrolyte particulate material in the conductor dispersion was 60wt%, the solid content of the nanocarbon material was 0.3wt%, and the mass fraction of the dispersant was 0.3wt%.
Example 3
This example is substantially the same as example 1 except that the mass of LATP in this example is 10g and the mass of carbon nanotubes is 40g.
Example 4
This example is substantially the same as example 1 except that the mass of LATP in this example is 160g and the mass of carbon nanotubes is 0.2g.
Example 5
This example is essentially the same as example 1, except that Li is used in this example 0.5 La 0.5 TiO 3 LATP in example 1 was replaced.
Example 6
This example is substantially the same as example 1 except that ketjen black is used in place of the carbon nanotubes in example 1.
Example 7
This example is substantially the same as example 1 except that the ball milling rate after mixing the LATP with the carbon nanotubes in this example is 500r/min.
Example 8
This example is substantially the same as example 1 except that the ball milling rate after mixing the LATP with the carbon nanotubes in this example is 1000r/min.
Example 9
This example is substantially the same as example 1 except that the high-energy ball mill in this example has a ball milling rate of 50r/min.
Example 10
This example is substantially the same as example 1 except that the high-energy ball mill in this example has a ball milling rate of 500r/min.
Example 11
This example is substantially the same as example 1 except that the ball milling time of the high energy ball mill in this example is 0.5h.
Example 12
This example is substantially the same as example 1 except that the ball milling time of the high energy ball mill in this example is 12 hours.
Comparative example
This comparative example provides a powder, weighing 2gLi 1.3 Al 0.3 Ti 1.7 P 3 O 12 0.05g of carbonThe nano-tube is obtained by mechanical mixing.
Battery example 1
The embodiment of the battery provides a button cell, and the preparation method comprises the following steps:
weighing 46.5g of positive electrode material nickel cobalt lithium manganate LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811), 5g of the conductor dispersion liquid provided in example 1, 0.225g of carbon nano tube, 15g of polyvinylidene fluoride glue solution with mass fraction of 5% and N-methyl pyrrolidone solvent are mixed, and ball milling is carried out for 3 hours at the speed of 350r/min, so as to obtain positive electrode slurry; coating the slurry on aluminum foil, baking for 2 hours in a 60 ℃ oven, primarily drying the pole piece, and then transferring the pole piece into a vacuum oven with the vacuum degree less than or equal to 133Pa, and drying for 12 hours at 120 ℃ to obtain a positive pole piece;
and cutting the anode plate into a wafer of Cheng mm, weighing the mass, and assembling the wafer with a lithium metal anode plate of phi 16mm and an oxide solid electrolyte LATP plate in a glove box filled with argon.
Battery examples 2 to 12
Battery examples 2 to 12 were substantially the same as battery example 1, except that the conductor dispersion liquid of battery example 1 was replaced with the conductor dispersion liquid of examples 2 to 12.
Battery example 13
The embodiment of the battery provides a button cell, and the preparation method comprises the following steps:
44.3g of positive electrode material lithium cobalt oxide LiCoO was weighed 2 10g of the conductor dispersion liquid provided in the example 1, 0.675g of carbon nano tube, 13g of polyvinylidene fluoride glue solution with mass fraction of 5% and N-methyl pyrrolidone solvent are mixed, ball milling is carried out for 3 hours at the speed of 350r/min, and then anode slurry is obtained; coating the slurry on aluminum foil, baking for 2 hours in a 60 ℃ oven, primarily drying the pole piece, and then transferring the pole piece into a vacuum oven with the vacuum degree less than or equal to 133Pa, and drying for 12 hours at 120 ℃ to obtain a positive pole piece; wherein the mass ratio of the positive electrode material to the inorganic electrolyte particles to the nano carbon material to the binder polyvinylidene fluoride is 88.6:10:0.1:1.3;
and cutting the anode plate into a wafer of Cheng mm, weighing the mass, and assembling the wafer with a lithium metal anode plate of phi 16mm and an oxide solid electrolyte LATP plate in a glove box filled with argon.
Battery example 14
Cell example 14 was essentially the same as cell example 2, except that lithium cobaltate LiCoO was used 2 Substitution cell example 2 lithium nickel cobalt manganese oxide LiNi 0.8 Co 0.1 Mn 0.1 O 2 。
Comparative example of cell
The battery comparative example was substantially the same as battery example 1 except that the powder of the comparative example was used instead of the conductor dispersion of battery example 1.
The positive electrode sheet of the battery example 1 was subjected to scanning electron microscope test to obtain a microscopic morphology graph of the positive electrode sheet, and the result is shown in fig. 2.
As can be seen from FIG. 2, the structure of the positive electrode sheet is uniform, and no large-area aggregation occurs.
Scanning electron microscope tests were performed on the positive electrode sheet of the battery example 1 to obtain mapping spectra of carbon element and titanium element in the positive electrode sheet, and the results are shown in fig. 3 and 4.
As can be seen from fig. 3, carbon elements are uniformly distributed in the gaps between the positive electrode particles in the positive electrode sheet in the battery example 1, and no agglomeration phenomenon occurs, which indicates that the conductor dispersion liquid plays a key role in the preparation of the positive electrode homogenate and the construction of a good electronic network inside the positive electrode.
As can be seen from fig. 4, titanium element was uniformly distributed in the gaps between the positive electrode particles in the positive electrode sheet in battery example 1, and agglomeration of titanium element occurred somewhere did not occur, which suggests that LATP particles in the conductor dispersion were not re-agglomerated into secondary particles, and that LATP was well dispersed inside the positive electrode and built up a good lithium ion conductive network inside the positive electrode during the positive electrode slurry coating.
The batteries of battery example 1 and battery comparative example were subjected to a normal temperature cycle retention test, and the changes in specific capacity and coulombic efficiency of the batteries with the number of cycles were obtained as shown in fig. 5.
As can be seen from fig. 5, the battery of example 1 had better normal temperature cycle retention than the battery of comparative example 1, mainly due to the good construction of the ion-electron channels inside the positive electrode of example 1 and the uniform dispersion of the electron ion conductors.
The battery of battery example 1 was subjected to charge and discharge tests, and graphs of the second and third turns of battery example 1 were obtained as shown in fig. 6.
As can be seen from fig. 6, the charge-discharge curves of the second and third turns of the battery in example 1 of the battery show typical high nickel to metallic lithium characteristics, which indicates that the inactive material does not cause greater polarization to the battery and the capacity of the battery is not affected.
The conductor dispersion liquid, the preparation method, the positive electrode plate and the solid-state battery provided by the embodiment of the application are described in detail, and specific examples are applied to the description of the principle and the implementation mode of the application, and the description of the examples is only used for helping to understand the method and the core idea of the application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.

Claims (11)

1. A method for preparing a conductor dispersion, comprising the steps of:
providing inorganic electrolyte particles and a nano carbon material, mixing and dispersing the inorganic electrolyte particles and the nano carbon material to obtain pre-dispersed powder;
providing a dispersing agent and a solvent, and mixing the dispersing agent, the solvent and the pre-dispersed powder to obtain a conductor dispersion liquid.
2. The method for producing a conductor dispersion according to claim 1, wherein,
the mass ratio of the inorganic electrolyte particles to the nano carbon material is (0.25-800): 1, a step of; and/or
In the conductor dispersion liquid, the solid content of the inorganic electrolyte particles is 5-80 wt%; and/or
In the conductor dispersion liquid, the solid content of the nano carbon material is 0.1-20wt%; and/or
In the conductor dispersion liquid, the mass fraction of the dispersing agent is 0.01-2 wt%.
3. The method for producing a conductor dispersion liquid according to claim 1, wherein the material of the inorganic electrolyte particles comprises one or more of a perovskite type material, a NASICON type material, a garnet type material, and a lithium phosphorus oxygen nitrogen type material; and/or
Average particle diameter D of the inorganic electrolyte particles 50 5-1000 nm; and/or
The nano carbon material comprises one or more of carbon black, acetylene black, carbon nano tubes, graphene, ketjen black and vapor phase growth carbon fibers; and/or
The structure of the nano carbon material comprises one or more of a punctiform structure, an amorphous structure, a sheet-shaped structure, a tubular structure, a linear structure and a spherical structure; and/or
The dispersing agent comprises one or more of a non-polymer dispersing agent and a polymer dispersing agent; and/or
The solvent comprises an aprotic polar solvent.
4. A method of preparing a conductor dispersion according to claim 3, wherein the perovskite-type material comprises Li a La b Ti c A d O e Wherein a is more than 0 and less than or equal to 0.5, b is more than 0 and less than or equal to 0.6,0.9, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.25,2 and e is less than or equal to 3, and A comprises one or more of Ba, sr and Al; and/or
The NASICON type material comprises Li f B g P h O 12 Wherein f is more than or equal to 1 and less than or equal to 3, g is more than or equal to 0 and less than or equal to 4, h is more than or equal to 1 and less than or equal to 3, and B comprises one or more than one of Al, zr, ti, ge, si; and/or
The garnet-type material comprises Li i La j Zr k C l O 12 Wherein i is more than 5 and less than or equal to 7, j is more than 2 and less than or equal to 3, and k is more than 1 and less than or equal to 20 < l < 1, C comprises one or more of Al, nb, ca, W, ta; and/or
The lithium phosphorus oxygen nitrogen material comprises LiPON; and/or
The non-polymer dispersing agent comprises one or more of dodecyl maltoside, cetyl trimethyl ammonium bromide, bile acid salt and steroid zwitterionic surfactant; and/or
The polymer type dispersing agent comprises one or more of alkylphenol ethoxylates, wholly aromatic polyamide, semi-aromatic polyamide and polyvinylpyrrolidone; and/or
The aprotic polar solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, acetone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile and hexamethylphosphoric triamide.
5. The method for producing a conductor dispersion liquid according to claim 1, wherein the method for dispersion is a method in which the inorganic electrolyte particles and the nanocarbon material after the mixing are subjected to first grinding by a grinding medium; and/or
The dispersant, the solvent and the pre-dispersed powder are mixed and then further comprise: and carrying out second grinding on the mixed dispersing agent, solvent and pre-dispersed powder through a grinding medium.
6. The method of preparing a conductor dispersion according to claim 5, wherein the grinding medium comprises one or more of zirconia beads, zirconium beads, glass beads; and/or
The average grain diameter of the grinding medium is 0.03-5 mm; and/or
The first grinding and the second grinding respectively and independently comprise one or more of high-energy ball mill grinding, mechanical stirrer grinding, vertical stirrer grinding and sand mill grinding.
7. A conductor dispersion prepared by the method for preparing a conductor dispersion according to any one of claims 1 to 6.
8. A positive electrode sheet comprising a positive electrode material, a first nanocarbon material, a binder, and the conductor dispersion liquid prepared by the method for preparing a conductor dispersion liquid according to any one of claims 1 to 6.
9. The positive electrode sheet of claim 8, wherein the positive electrode sheet comprises a carbon electronic conductor material comprising the first nanocarbon material and the nanocarbon material in the conductor dispersion;
in the positive electrode sheet, the mass ratio of the positive electrode material to the inorganic electrolyte particles to the carbon electron conductor material to the binder is (87-99.5): (0.1-10): (0.1-1.5): (0.3-1.5).
10. The positive electrode sheet of claim 8, wherein the positive electrode material comprises one or more of lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese phosphate, lithium nickel manganese oxide, sulfur material, polymer-sulfur material; and/or
The binder comprises one or more of polyvinylidene fluoride, polyacrylonitrile, styrene-butadiene latex, polyimide, hydroxymethyl cellulose, polytetrafluoroethylene emulsion, polyacrylate, hydrogenated nitrile rubber and polyurethane.
11. A solid state battery comprising a negative electrode sheet, a solid state electrolyte and a positive electrode sheet according to any one of claims 8 to 10.
CN202310423744.3A 2023-04-17 2023-04-17 Conductor dispersion liquid, preparation method, positive electrode plate and solid-state battery Pending CN116469601A (en)

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Publication number Priority date Publication date Assignee Title
CN103474620A (en) * 2013-09-16 2013-12-25 向勇 Solid-state lithium ion electrode, solid-state lithium ion battery and preparation method of solid-state lithium ion electrode
JP2018195372A (en) * 2017-05-12 2018-12-06 日立化成株式会社 Electrode composition for lithium ion battery, lithium ion battery electrode and lithium ion battery using the composition, and method of manufacturing lithium ion battery electrode
CN109301314A (en) * 2017-07-24 2019-02-01 微宏动力系统（湖州）有限公司 A kind of preparation method and inorganic solid electrolyte composite mortar of inorganic solid electrolyte composite mortar
CN110415888A (en) * 2019-06-14 2019-11-05 江西力能新能源科技有限公司 A kind of carbon nanotube oil series conductive slurry and preparation method thereof containing solid electrolyte

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474620A (en) * 2013-09-16 2013-12-25 向勇 Solid-state lithium ion electrode, solid-state lithium ion battery and preparation method of solid-state lithium ion electrode
JP2018195372A (en) * 2017-05-12 2018-12-06 日立化成株式会社 Electrode composition for lithium ion battery, lithium ion battery electrode and lithium ion battery using the composition, and method of manufacturing lithium ion battery electrode
CN109301314A (en) * 2017-07-24 2019-02-01 微宏动力系统（湖州）有限公司 A kind of preparation method and inorganic solid electrolyte composite mortar of inorganic solid electrolyte composite mortar
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