CN116314755B - Composite positive electrode material, preparation method thereof, positive electrode plate and solid-state battery - Google Patents
Composite positive electrode material, preparation method thereof, positive electrode plate and solid-state battery Download PDFInfo
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- CN116314755B CN116314755B CN202310320720.5A CN202310320720A CN116314755B CN 116314755 B CN116314755 B CN 116314755B CN 202310320720 A CN202310320720 A CN 202310320720A CN 116314755 B CN116314755 B CN 116314755B
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- Prior art keywords
- positive electrode
- coupling agent
- composite
- active material
- composite positive
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 129
- 239000003792 electrolyte Substances 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 37
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 43
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- 238000000034 method Methods 0.000 claims description 30
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 27
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- 229910052744 lithium Inorganic materials 0.000 claims description 10
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- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 5
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
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- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
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- 239000006230 acetylene black Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 3
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
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- 229910020717 Li0.33La0.56TiO3 Inorganic materials 0.000 description 1
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- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
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- 229910009461 Li1.4Ti2Si0.4P2.6O12 Inorganic materials 0.000 description 1
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- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a composite positive electrode material and a preparation method thereof, a positive electrode plate and a solid-state battery, and relates to the technical field of solid-state batteries, wherein the preparation method comprises the following steps: mixing an anode active material and inorganic electrolyte particles to obtain a powder material; dispersing the powder material in a first solvent to obtain a dispersion liquid; mixing an alcohol aqueous solution and a coupling agent to obtain an intermediate solution, wherein the coupling agent is a coupling agent capable of generating hydroxyl by hydrolysis; and mixing the dispersion liquid and the intermediate solution for reaction to obtain the composite positive electrode material. According to the preparation method disclosed by the application, the hydrolyzable coupling agent vinyl coupling agent and the epoxy coupling agent are added, and the coupling agent is used for modifying the powder material, so that the composite material with dispersion uniformity and stability is prepared. The application also discloses the composite positive electrode material prepared by the preparation method, a positive electrode plate containing the composite positive electrode material and a solid-state battery.
Description
Technical Field
The present disclosure relates to the field of solid-state batteries, and more particularly, to a method for preparing a composite positive electrode material, a composite positive electrode material prepared by the method, a positive electrode sheet containing the composite positive electrode material, and a solid-state battery containing the positive electrode sheet.
Background
Currently, commercial liquid lithium ion batteries are facing great challenges in terms of safety, extreme use conditions, and other application end, as well as in terms of energy density, coulombic efficiency, service life, and other performance end, and thus researchers are greatly developing solid-state batteries based on solid electrolytes. A solid-state battery is a battery using a solid electrode and a solid electrolyte having a density and a structure that allows more charged ions to accumulate at one end, conducting a larger current, and thus improving battery capacity. Compared with a liquid battery, the solid electrolyte in the solid battery has the advantages of incombustibility, wide temperature use window, high chemical stability, wide electrochemical window, higher hardness and strength and the like, so that the solid battery has the characteristics of high energy density, small volume and safety, accords with the development direction of a large-capacity secondary battery in the future, and is an ideal power supply for large-scale energy storage.
However, the slow ion transport kinetics inside the positive electrode of a solid-state lithium battery severely restricts the performance exertion, so that the construction of a lithium ion conduction network inside the positive electrode by adding an ion conductor is one of the key problems to be considered in designing a solid-state battery system with good performance. Many studies are currently performed to construct a lithium ion transport path by introducing plasticizers such as ionic liquids, plastic crystals, or solid electrolytes including oxides, organics, sulfides, halides, etc. into a composite positive electrode using mechanical mixing, casting, or hot pressing. The addition of the inorganic oxide solid electrolyte with high ionic conductivity is a common strategy for constructing an ionic conduction network in the composite positive electrode at present because of the advantages of simple mixing mode, inhibition of transition metal dissolution of active materials, inhibition of side reaction under high voltage, change of components of a passivation layer on the surface of the cathode, and the like. In the preparation of the composite positive electrode of the prior art, most of inorganic electrolyte conductors and active materials are only purely physically mixed and have no chemical interaction, so that the proportion of positive electrode active materials is generally low when a battery is designed, and the energy density of a pole piece is difficult to improve; in addition, the problems of interface degradation, large charge diffusion barrier and the like caused by the expansion and contraction of the volume of the positive electrode material and side reaction in the working process of the battery are solved, so that the transmission of lithium ions is prevented, the internal resistance of the battery is increased, and the capacity of the battery is finally quickly attenuated. Meanwhile, when the inorganic solid electrolyte with smaller particle size, especially nano size is used for constructing the composite positive electrode, the problems of agglomeration of internal materials of the composite positive electrode, interface contact among particles, poor stability and the like are unavoidable.
Therefore, a method for constructing a solid composite anode with good contact and high active material loading by a simple process is needed, so that a continuous and rapid lithium ion migration channel is constructed in the composite anode, the dispersibility and electrochemical stability of each material of the composite anode are improved, and the capacity retention rate and the cycling stability of the solid battery are improved.
Disclosure of Invention
In view of the above, the application provides a composite positive electrode material, a preparation method thereof, a positive electrode plate and a solid-state battery, and aims to solve the problem that the dispersibility of the existing positive electrode material is not high.
The embodiment of the application is realized in such a way that the preparation method of the composite positive electrode material comprises the following steps:
mixing an anode active material and inorganic electrolyte particles to obtain a powder material;
dispersing the powder material in a first solvent to obtain a dispersion liquid;
mixing an alcohol aqueous solution and a coupling agent to obtain an intermediate solution, wherein the coupling agent is a coupling agent capable of generating hydroxyl by hydrolysis;
and mixing the dispersion liquid and the intermediate solution for reaction to obtain the composite positive electrode material.
Alternatively, in some embodiments of the present application, the coupling agent that is hydrolyzable to produce hydroxyl groups includes at least one of a vinyl coupling agent and an epoxy coupling agent.
Optionally, in some embodiments of the present application, the vinyl coupling agent comprises at least one of a vinyl silane coupling agent, a vinyl titanate coupling agent, a vinyl aluminate coupling agent, a vinyl borate coupling agent; and/or
The epoxy coupling agent comprises at least one of epoxy silane coupling agent, epoxy titanate coupling agent, epoxy aluminate coupling agent and epoxy borate coupling agent; and/or
The positive electrode active material comprises at least one of lithium cobaltate, lithium nickel manganate, lithium iron phosphate and lithium nickel cobalt manganate; and/or
Average particle diameter D of the positive electrode active material 50 0.5-100 mu m; and/or
The material of the inorganic electrolyte particles comprises at least one of sulfide solid electrolyte, polymer solid electrolyte, borohydride solid electrolyte, halide solid electrolyte and oxide solid electrolyte; and/or
Average particle diameter D of the inorganic electrolyte particles 50 10-1000 nm; and/or
The first solvent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The alcohol substance in the alcohol water solution comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The intermediate solution comprises a silane coupling agent and silanol.
Optionally, in some embodiments of the present application, the mass ratio of the inorganic electrolyte particles to the positive electrode active material is (0.1 to 40): (60-99.9); and/or
The mass ratio of the powder material to the coupling agent is (70-99.9): (0.1-30); and/or
In the dispersion liquid, the mass concentration of the powder material is 0.1-2 g/mL; and/or
In the alcohol water solution, the mass concentration of the alcohol substances is 95% -99%; and/or
The mass fraction of the coupling agent in the intermediate solution is 5% -25%.
Optionally, in some embodiments of the present application, after mixing the positive electrode active material and the inorganic electrolyte particles, the method further includes performing a first ball milling treatment, where a ball milling rate of the first ball milling treatment is 300-350 r/min, and a ball milling time of the ball milling treatment is 0.5-1 h; and/or
The dispersing method comprises ultrasonic dispersing, wherein the frequency of the ultrasonic dispersing is 30-50 kHz, and the time of the ultrasonic dispersing is 20-40 min; and/or
The mixing method is that the first stirring is carried out, the speed of the first stirring is 400-1200 r/min, and the time of the first stirring is 5-20 min; and/or
The second stirring is carried out after the dispersion liquid and the intermediate solution are mixed, the speed of the second stirring is 400-1200 r/min, the time of the second stirring is 2-6 h, and the second stirring is carried out at the temperature of 30-80 ℃.
Optionally, in some embodiments of the present application, after the second stirring, further including centrifugal separation washing and vacuum drying with a detergent to obtain a composite cathode material;
wherein the detergent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The centrifugal separation speed is 5000-8000 r/min, and the centrifugal separation time is 3-5 min; and/or
The temperature of the vacuum drying is 30-200 ℃; the time of vacuum drying is 1-48 h.
Correspondingly, the application also provides a composite positive electrode material which comprises inorganic electrolyte particles modified by a coupling agent and a positive electrode active material, wherein the coupling agent is a coupling agent capable of generating hydroxyl by hydrolysis.
Alternatively, in some embodiments of the present application, the coupling agent that is hydrolyzable to produce hydroxyl groups includes at least one of a vinyl coupling agent and an epoxy coupling agent.
Optionally, in some embodiments of the present application, the vinyl coupling agent comprises at least one of a vinyl silane coupling agent, a vinyl titanate coupling agent, a vinyl aluminate coupling agent, a vinyl borate coupling agent; and/or
The epoxy coupling agent comprises at least one of epoxy silane coupling agent, epoxy titanate coupling agent, epoxy aluminate coupling agent and epoxy borate coupling agent; and/or
The positive electrode active material comprises at least one of lithium cobaltate, lithium nickel manganate, lithium iron phosphate and lithium nickel cobalt manganate; and/or
Average particle diameter D of the positive electrode active material 50 0.5-100 mu m; and/or
The material of the inorganic electrolyte particles comprises at least one of sulfide solid electrolyte, polymer solid electrolyte, borohydride solid electrolyte, halide solid electrolyte and oxide solid electrolyte; and/or
Average particle diameter D of the inorganic electrolyte particles 50 Is 10-1000 nm.
Optionally, in some embodiments of the present application, the mass ratio of the inorganic electrolyte particles to the positive electrode active material is (0.1 to 40): (60-99.9); and/or
The mass ratio of the mass sum of the inorganic electrolyte particles and the positive electrode active material to the coupling agent is (70 to 99.9): (0.1-30).
Correspondingly, the application also provides a positive electrode plate, which comprises a conductive material, a binder and the composite positive electrode material prepared by the preparation method, or the composite positive electrode material.
Optionally, in some embodiments of the present application, the conductive material includes at least one of conductive carbon black, conductive graphite, acetylene black, carbon nanotubes, carbon nanofibers, ketjen black; and/or
The binder comprises at least one of polyvinylidene fluoride, polyacrylonitrile, styrene-butadiene latex, polyimide, hydroxymethyl cellulose, polytetrafluoroethylene emulsion, polyacrylate, hydrogenated nitrile rubber and polyurethane.
Optionally, in some embodiments of the present application, in the positive electrode sheet, a mass ratio of the composite positive electrode material, the conductive material, and the binder is (80-97.2): (2.3-10): (0.5-10).
Correspondingly, the application also provides a solid-state battery, which comprises a negative electrode plate, a solid electrolyte and the positive electrode plate.
Optionally, in some embodiments of the present application, the negative electrode sheet includes at least one of a graphite negative electrode, a metallic lithium negative electrode, a silicon-based negative electrode, a silicon-graphite composite negative electrode, a metallic lithium alloy negative electrode, a copper foil lithium-free negative electrode; and/or
The solid electrolyte includes at least one of a sulfide electrolyte, an oxide electrolyte, a halide electrolyte, a polymer electrolyte, or a composite electrolyte.
According to the preparation method of the composite positive electrode material, the powder material is modified by adding the coupling agent capable of generating hydroxyl through hydrolysis, so that the composite material with dispersion uniformity and stability is prepared, and the coupling agent capable of generating hydroxyl through hydrolysis comprises a vinyl coupling agent and an epoxy coupling agent. On one hand, the products of the hydrolysis of the vinyl coupling agent and the epoxy coupling agent have hydroxyl groups with stronger polarity, the hydrolyzed products can be subjected to condensation dehydration reaction with hydroxyl groups rich in the surfaces of oxide type inorganic electrolyte particles to form covalent bonds, and the firm chemical bonding effect can effectively inhibit the aggregation of the inorganic electrolyte particles in the positive electrode slurry, so that the dispersion uniformity and stability of a positive electrode system are improved; on the other hand, the vinyl coupling agent and the epoxy coupling agent play a bridging role between the positive electrode active material and the inorganic electrolyte, and can realize close contact between the positive electrode active material and the inorganic electrolyte particles in the positive electrode system through polycondensation reaction, so that the positive electrode active material can adapt to volume deformation of the positive electrode active material in the charge and discharge process, the structural stability of the positive electrode plate during operation is improved, and the cycling stability of the battery is improved. In addition, the selected inorganic electrolyte has the characteristics of small particle size, good toughness, large specific surface area and the like, and forms good interface contact with the activity of the positive electrode under the bridging action of the coupling agent, and only a small amount of the inorganic electrolyte is added, so that the high-load composite positive electrode plate can be obtained, a continuous and effective lithium ion conduction path can be built in the positive electrode, and the lithium ion conduction efficiency in the composite positive electrode is improved.
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 preparation method of a composite positive electrode material provided in an embodiment of the present application;
FIG. 2 is a transmission electron microscope image of the composite positive electrode material of example 1 of the present application;
FIG. 3 is a scanning electron microscope image of the positive electrode sheet of example 1 of the battery of the present application;
fig. 4 is a graph of the cycle performance of battery example 1 of the present application at 0.5C current.
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. "at least one", "at least one" 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 composite positive electrode material, including the following steps:
step S11: mixing an anode active material and inorganic electrolyte particles to obtain a powder material;
step S12: dispersing the powder material in a first solvent to obtain a dispersion liquid;
step S13: mixing an alcohol aqueous solution and a coupling agent to obtain an intermediate solution, wherein the coupling agent is a coupling agent capable of generating hydroxyl by hydrolysis;
Step S14: and mixing the dispersion liquid and the intermediate solution for reaction to obtain the composite positive electrode material.
In the step S11:
in some embodiments, the coupling agent that is hydrolyzable to produce hydroxyl groups includes at least one of a vinyl coupling agent and an epoxy coupling agent.
In some embodiments, the positive electrode active material includes at least one of lithium cobaltate, lithium nickel manganate, lithium iron phosphate, lithium nickel cobalt manganate.
In some embodiments, the average particle diameter D of the positive electrode active material 50 For example, the thickness may be 1 to 90. Mu.m, 10 to 80. Mu.m, 20 to 70. Mu.m, 50 to 60. Mu.m, or the like, in the range of 0.5 to 100. Mu.m. The positive electrode active material and the inorganic electrolyte particles have good interface contact within the particle size range.
In some embodiments, the material of the inorganic electrolyte particles includes at least one of a sulfide solid state electrolyte, a polymer solid state electrolyte, a borohydride solid state electrolyte, a halide solid state electrolyte, an oxide solid state electrolyte.
The oxide solid electrolyte includes at least one of perovskite type material, NASICON type material, and garnet type material.
The perovskite type material comprises 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 At least one of them.
The NASICON type material comprises 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 Al0.5Ge 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 、Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 -AIPO 4 And Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 At least one of them.
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 At least one of them.
In some embodiments, the inorganic electrolyte particles have an average particle size D 50 The particle size may be 10 to 1000nm, for example, 50 to 800nm,100 to 600 nm,200 to 500nm,300 to 400nm, 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 positive electrode active material.
In some embodiments, the mass ratio of the inorganic electrolyte particles to the positive electrode active material is (0.1 to 40): (60 to 99.9), for example, (1 to 35): (65-99), (5-30): (70-95), (10-25): (75-90), (12-22): (78-88), (15-20): (80-85), and the like. In the range of the mass ratio, the inorganic electrolyte can effectively ensure the construction of the porous positive electrode ion transmission network.
In some embodiments, after mixing the positive electrode active material and the inorganic electrolyte particles, further comprising performing a first ball milling process.
In some embodiments, the ball milling rate of the first ball milling treatment is 300-350 r/min, for example, 305-345 r/min, 310-340 r/min, 315-335 r/min, 320-330 r/min, etc.; the ball milling time is 0.5 to 1h, for example, 0.55 to 0.95h,0.6 to 0.9h,0.65 to 0.85h,0.7 to 0.8h, etc. The inorganic electrolyte particles can be effectively crushed and uniformly dispersed among the active material particles within the rate and time range of the first ball milling.
In the step S12:
in some embodiments, the first solvent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, pentanol, hexanol, n-butanol, isopropanol.
In some embodiments, the mass concentration of the powder material in the dispersion is 0.1 to 2g/mL, for example, 0.2 to 1.8g/mL,0.3 to 1.7g/mL,0.4 to 1.6g/mL,0.5 to 1.5g/mL,0.8 to 1g/mL, and the like. Within the mass concentration range, the powder material may be uniformly dispersed in the first solvent.
In some embodiments, the dispersing method includes known dispersing methods such as ultrasonic dispersing or stirring dispersing.
The ultrasonic dispersion frequency is 30-50 kHz, and can be 32-48 kHz, 33-46 kHz, 35-45 kHz, 36-44 kHz, 38-42 kHz, etc.; the ultrasonic dispersion time is 20 to 40 minutes, for example, 22 to 38 minutes, 23 to 36 minutes, 25 to 32 minutes, 26 to 31 minutes, 28 to 30 minutes, and the like. The dissolution and dispersion of the powder material in the first solvent may be promoted within the frequency and time range of the ultrasonic dispersion.
In the step S13:
in some embodiments, the vinyl coupling agent comprises at least one of a vinyl silane coupling agent, a vinyl titanate coupling agent, a vinyl aluminate coupling agent, a vinyl borate coupling agent.
In some embodiments, the epoxy-based coupling agent includes at least one of an epoxy-based silane coupling agent, an epoxy-based titanate coupling agent, an epoxy-based aluminate coupling agent, an epoxy-based borate coupling agent.
In some embodiments, the mass ratio of the powder material to the coupling agent is (70-99.9): (0.1 to 30), for example, (72 to 98): (2-28), (74-96): (4-26), (78-94): (6-22), (80-90): (10-20), (82-88): (12-18), and the like. In the mass ratio range, the coupling agent can be uniformly coated on the inorganic electrolyte and the active material, and the hydrolysate of the coupling agent can effectively inhibit the aggregation of the inorganic electrolyte particles in the powder material, so that the dispersion uniformity and stability of the composite positive electrode material are improved. In some embodiments, the aqueous alcohol solution includes water and an alcohol including at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, pentanol, hexanol, n-butanol, isopropanol.
In some embodiments, the mass concentration of the alcohol substance in the alcohol aqueous solution is 95% -99%, for example, 95.5% -98.5%, 95.6% -98.2%, 96% -98%, 96.2% -97.5%, 96.5% -97%, etc. In the mass concentration range, the alcohol substance content is higher, so that the sufficient hydrolysis of the coupling agent can be promoted.
In some embodiments, the mass fraction of the coupling agent in the intermediate solution is 5% to 25%, for example, may be 8% to 22%,9% to 21%,10% to 20%,11% to 19%,13% to 18%, etc. Within the mass concentration range, sufficient hydrolysis of the coupling agent may be achieved.
In some embodiments, the method of mixing is a first agitation. The first stirring speed is 400-1200 r/min, for example, 500-1100 r/min, 550-1050 r/min, 600-1000 r/min, 650-950 r/min, 700-900 r/min and the like; the time is 5 to 20 minutes, for example, 8 to 18 minutes, 9 to 17 minutes, 10 to 16 minutes, 11 to 15 minutes, 12 to 14 minutes, and the like. Hydrolysis of the coupling agent may be promoted within the rate and time frame of the first agitation.
In some embodiments, the intermediate solution includes a silane coupling agent and a silanol.
In the step S14:
in some embodiments, mixing the dispersion with the intermediate solution further comprises performing a second agitation.
The second stirring speed is 400-1200 r/min, for example, 500-1100 r/min, 550-1050 r/min, 600-1000 r/min, 650-950 r/min, 700-900 r/min and the like; the time is 2 to 6 hours, for example, 2.2 to 5.8 hours, 2.5 to 5.5 hours, 3 to 5 hours, 3.2 to 4.5 hours, 3.5 to 4 hours, etc. The mixing of the dispersion and the intermediate solution may be promoted within the speed and time range of the second stirring.
In some embodiments, the second agitation is performed at a temperature of 30-80 ℃, such as 35-75 ℃, 40-70 ℃, 45-65 ℃, 50-60 ℃, 52-55 ℃, and the like. The mixing reaction of the dispersion and the intermediate solution can thus be more sufficient.
In some embodiments, after the second agitating, further comprising subjecting the composite positive electrode material to centrifugal washing and vacuum drying using a detergent. Washing may wash away some unreacted monomers and byproducts and products that are not coated on the particle surface.
In some embodiments, the rate of centrifugation is 5000-8000 r/min, e.g., 5500-7500 r/min, 5800-7200 r/min, 6000-7000 r/min, 6100-6900 r/min, 6200-6800 r/min, etc.; the time is 3 to 5 minutes, for example, 3.2 to 4.8 minutes, 3.3 to 4.6 minutes, 3.5 to 4.5 minutes, 3.6 to 4.2 minutes, 3.8 to 4 minutes, etc.; the number of times of washing is 3 to 5, for example, 4 times. The purity of the composite positive electrode material may be improved in the range of the rate, time, and number of washing times of the centrifugal separation.
In some embodiments, the detergent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, butanol, pentanol, hexanol, n-butanol, isopropanol.
In some embodiments of the present invention, in some embodiments,
the vacuum drying temperature is 30-200deg.C, for example 40-180deg.C, 60-160deg.C, 80-150deg.C, 100-130deg.C, 110-120deg.C, etc.; the time for vacuum drying is 1 to 48 hours, and may be, for example, 5 to 45 hours, 10 to 40 hours, 15 to 35 hours, 20 to 30 hours, 25 to 28 hours, or the like. Under the conditions of the temperature and time of the vacuum drying, the solvent in the composite positive electrode material can be effectively removed, and the service performance of the composite positive electrode material can be effectively exerted.
According to the preparation method of the composite positive electrode material, the coupling agent capable of generating hydroxyl through hydrolysis is added, the coupling agent comprises a vinyl coupling agent and an epoxy coupling agent, and the powder material is modified through the coupling agent, so that the composite material with dispersion uniformity and stability is prepared. On the one hand, the products of the hydrolysis of the vinyl coupling agent and the epoxy coupling agent have hydroxyl groups with stronger polarity, the hydrolyzed products can be subjected to condensation dehydration reaction with hydroxyl groups rich in the surfaces of oxide type inorganic electrolyte particles to form covalent bonds, the firm chemical bonding effect can effectively inhibit the aggregation of the inorganic electrolyte particles in the positive electrode slurry, the dispersion uniformity and stability of the positive electrode system are improved, and the hydrolyzed products are subjected to chemical reaction with the hydroxyl groups on the surfaces of the positive electrode materials and are connected with the positive electrode materials; on the other hand, the vinyl coupling agent and the epoxy coupling agent play a bridging role between the positive electrode active material and the inorganic electrolyte, and can realize close contact between the positive electrode active material and the inorganic electrolyte particles in the positive electrode system through polycondensation reaction, so that the positive electrode active material can adapt to volume deformation of the positive electrode active material in the charge and discharge process, the structural stability of the positive electrode plate during operation is improved, and the cycling stability of the battery is improved. In addition, the selected inorganic electrolyte has the characteristics of small particle size, good toughness, large specific surface area and the like, and forms good interface contact with the activity of the positive electrode under the bridging action of the coupling agent, and only a small amount of the inorganic electrolyte is added, so that the high-load composite positive electrode plate can be obtained, a continuous and effective lithium ion conduction path can be built in the positive electrode, and the lithium ion conduction efficiency in the composite positive electrode is improved.
In a second aspect, embodiments of the present application also provide a composite positive electrode material made by the method of making a composite positive electrode material described above.
In some embodiments, the composite positive electrode material includes inorganic electrolyte particles modified with a coupling agent and a positive electrode active material.
The coupling agent, the positive electrode active material, and the inorganic electrolyte particles are described above, and are not described here.
The composite positive electrode material comprises inorganic electrolyte particles modified by a coupling agent which generates hydroxyl through hydrolysis and a positive electrode active material, wherein the coupling agent which generates hydroxyl through hydrolysis comprises a vinyl coupling agent and an epoxy coupling agent. On one hand, the products of the hydrolysis of the vinyl coupling agent and the epoxy coupling agent have hydroxyl groups with stronger polarity, the hydrolyzed products can be subjected to condensation dehydration reaction with hydroxyl groups rich in the surfaces of oxide type inorganic electrolyte particles to form covalent bonds, and the firm chemical bonding effect can effectively inhibit the aggregation of the inorganic electrolyte particles in the positive electrode slurry, so that the dispersion uniformity and stability of a positive electrode system are improved; on the other hand, the vinyl coupling agent and the epoxy coupling agent play a bridging role between the positive electrode active material and the inorganic electrolyte, and can realize close contact between the positive electrode active material and the inorganic electrolyte particles in the positive electrode system through polycondensation reaction, so that the positive electrode active material can adapt to volume deformation of the positive electrode active material in the charge and discharge process, the structural stability of the positive electrode plate during operation is improved, and the cycling stability of the battery is improved. In addition, the selected inorganic electrolyte has the characteristics of small particle size, good toughness, large specific surface area and the like, and forms good interface contact with the activity of the positive electrode under the bridging action of the coupling agent, and only a small amount of the inorganic electrolyte is added, so that the high-load composite positive electrode plate can be obtained, a continuous and effective lithium ion conduction path can be built in the positive electrode, and the lithium ion conduction efficiency in the composite positive electrode is improved.
In a third aspect, embodiments of the present application further provide a positive electrode sheet, including a conductive material, a binder, and a composite positive electrode material described above, or a composite positive electrode material prepared by the preparation method described above.
In some embodiments, the conductive material comprises at least one of conductive carbon black, conductive graphite, acetylene black, carbon nanotubes, carbon nanofibers (VGCF), ketjen black.
In some embodiments, the binder includes at least one 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 conductive material, a binder, a solvent and the composite positive electrode material, 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 conductive material, a binder, a solvent and the composite anode material, mixing, and performing a second ball milling treatment to obtain anode slurry.
The second ball milling treatment speed is 300-350 r/min, for example, 310-345 r/min, 315-340 r/min, 320-335 r/min, 325-330 r/min, etc.; the second ball milling treatment 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, 2.5 to 2.5 hours, and the like. Mixing of the conductive material, the binder, the solvent, and the composite positive electrode material may be promoted within the rate and time range of the second ball milling process.
In other embodiments, the method of preparing the positive electrode slurry includes: providing a binder and the composite positive electrode material, and carrying out first premixing stirring; adding conductive material to perform second premixing stirring; adding a solvent for kneading and stirring; and adding the solvent for dilution stirring, defoaming stirring and obtaining the anode slurry.
The speed of the first premixed stirring is 5 to 20rpm, for example, 8 to 18rpm,9 to 17rpm,10 to 16rpm,11 to 15rpm,12 to 14rpm, etc.; the time of the first premixing and stirring is 5 to 10min, for example, 5.5 to 9.5min,6 to 9min,6.5 to 8.5min,7 to 8min, and the like. The binder and the composite positive electrode material may be promoted to be sufficiently mixed within a rate and time range of the first premixed stirring.
The second premixed stirring speed is 5 to 20rpm, for example, 8 to 18rpm,9 to 17rpm,10 to 16rpm,11 to 15rpm,12 to 14rpm, etc.; the second premixing and stirring time is 10 to 20 minutes, for example, 11 to 19 minutes, 12 to 18 minutes, 13 to 17 minutes, 14 to 16 minutes, 14.5 to 15 minutes, and the like. The conductive material and the binder, the composite positive electrode material may be promoted to be sufficiently mixed within the rate and time range of the second premixed stirring.
The kneading and stirring speed is 1500 to 2000rpm, and may be 1550 to 1900rpm,1600 to 1850rpm,1650 to 1700rpm, etc., for example; the kneading and stirring time is 30 to 60 minutes, and may be, for example, 35 to 55 minutes, 40 to 50 minutes, 42 to 48 minutes, and the like. Mixing of the conductive material, the binder, and the composite positive electrode material may be promoted in the rate and time range of the kneading agitation.
The dilution stirring speed is 1500-2000 rpm, for example 1550-1900 rpm, 1600-1800 rpm, 1650-1700 rpm, etc.; the time for the dilution and stirring is 20 to 30 minutes, for example, 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 positive electrode slurry after the dilution and stirring is 4000 to 5000 map.S, for example, 4500 to 700 map.S,5000 to 6500map.S,5500 to 600 map.S, or the like. In the viscosity range, the coating and drying of the positive electrode slurry can be facilitated.
The defoaming stirring speed is 50-100 rpm, for example, 55-90 rpm, 60-80 rpm, 65-70 rpm and the like; the defoaming and stirring time is 1-360 min, for example, 10-300 min, 20-260 min, 50-220 min, 100-200 min, 150-180 min 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, in the positive electrode sheet, the mass ratio of the composite positive electrode material, the conductive material, and the binder is (80-97.2): (2.3-10): (0.5-10). In the mass ratio range, the performance of the positive electrode active material is ensured under the condition that the composite positive electrode material and the conductive material can be effectively and uniformly dispersed.
In some embodiments, the solvent comprises at least one of N, N dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetramethylurea, trimethyl phosphate, dimethylacetamide.
In some embodiments, the drying includes baking and drying.
The baking temperature is 0 to 200 ℃, for example, 10 to 180 ℃,20 to 150 ℃,50 to 120 ℃,60 to 100 ℃,70 to 80 ℃ and the like; the baking time is 2 to 3 hours, for example, 2.2 to 2.8 hours, 2.3 to 2.7 hours, 2.4 to 2.6 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, 105-118 ℃, 108-115 ℃, 110-112 ℃ and the like; the vacuum drying time is 12 to 24 hours, for example, 13 to 22 hours, 14 to 21 hours, 15 to 20 hours, 16 to 19 hours, 17 to 18 hours, etc.; the vacuum degree of the vacuum drying is 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 comprises a coupling agent containing hydroxyl generated by hydrolysis, wherein the coupling agent containing hydroxyl generated by hydrolysis of a composite positive electrode material, a binder and a conductive material comprises a vinyl coupling agent and an epoxy coupling agent, on one hand, products of hydrolysis of the vinyl coupling agent and the epoxy coupling agent have hydroxyl with stronger polarity, the products of hydrolysis can be subjected to condensation dehydration reaction with hydroxyl rich in the surface of oxide type inorganic electrolyte particles to form covalent bonds, and the firm chemical bonding effect can effectively inhibit aggregation of inorganic electrolyte particles in positive electrode slurry, so that the dispersion uniformity and stability of a positive electrode system are improved; on the other hand, the vinyl coupling agent and the epoxy coupling agent play a bridging role between the positive electrode active material and the inorganic electrolyte, and can realize close contact between the positive electrode active material and the inorganic electrolyte particles in the positive electrode system through polycondensation reaction, so that the positive electrode active material can adapt to volume deformation of the positive electrode active material in the charge and discharge process, the structural stability of the positive electrode plate during operation is improved, and the cycling stability of the battery is improved. In addition, the selected inorganic electrolyte has the characteristics of small particle size, good toughness, large specific surface area and the like, and forms good interface contact with the activity of the positive electrode under the bridging action of the coupling agent, and only a small amount of the inorganic electrolyte is added, so that the high-load composite positive electrode plate can be obtained, a continuous and effective lithium ion conduction path can be built in the positive electrode, and the lithium ion conduction efficiency in the composite positive electrode is improved.
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 at least one of a graphite negative electrode, a metallic lithium negative electrode, a silicon-based negative electrode, a silicon-graphite composite negative electrode, a metallic lithium alloy negative electrode, a copper foil lithium-free negative electrode.
In some embodiments, the solid state electrolyte comprises at least one 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 、Li 7-x PS 6-x Cl x (x=0 to 2).
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 At least one 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 At least one of them.
The polymer electrolyte comprises at least one or a mixture of several 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), poly (1, 3-dioxolane) and polyethylene carbonate (PVC).
The composite electrolyte comprises more than two electrolytes formed by compositing the 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.
According to the solid-state battery provided by the embodiment of the application, the anode plate contains the composite anode material modified by the coupling agent capable of hydrolyzing to generate hydroxyl, the coupling agent capable of hydrolyzing to generate hydroxyl comprises the vinyl coupling agent or the epoxy coupling agent, so that the dispersion uniformity and stability of an anode system can be improved, a continuous and effective lithium ion conduction path is built in the anode, the lithium ion conduction efficiency in the composite anode is improved, the volume deformation of the anode active material in the charging and discharging process is adapted, the structural stability of the anode plate during working is improved, and the cycling stability of the battery is 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
This example provides a composite positive electrode material comprising inorganic electrolyte particles Li modified with a coupling agent gamma-methacryloxypropyl trimethoxysilane (KH 570) 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) and cathode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811). The preparation method of the composite positive electrode material comprises the following steps:
weighing 39.6g of NCM811 with the particle size of 8 mu m and 0.4g of LLZTO with the particle size of 50nm, and ball milling for 0.5h at the speed of 300r/min to obtain a powder material; ultrasonic treatment is carried out on the powder material for 20min at the frequency of 30kHz, and the powder material is dispersed in ethanol to obtain dispersion liquid, wherein the concentration of the powder material is 0.1g/mL;
the mass ratio of deionized water to ethanol is 0.1:99.9 preparing an alcohol water solution, stirring for 5min at the speed of 500r/min, and adding 10g of KH570 coupling agent during stirring to hydrolyze the KH570 coupling agent to obtain a KH570 coupling agent intermediate solution; wherein the mass fraction of KH570 coupling agent in the intermediate solution is 5%;
mixing the KH570 intermediate solution and the dispersion liquid, heating and stirring at 60 ℃ and a rotation speed of 400r/min for 3 hours, cooling to room temperature, centrifugally separating for 3 minutes by using an ethanol solvent at a rotation speed of 5000r/min, centrifugally separating and washing for 3 times, and vacuum drying at 60 ℃ for 6 hours to obtain the composite anode material.
Example 2
This example is substantially the same as example 1, except that in this example, the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811) substitution with LiCoO 2 。
Example 3
This example is essentially the same as example 1 except that KH570 coupling agent is replaced with gamma-glycidoxypropyl trimethoxysilane (A-187) coupling agent.
Example 4
This example is essentially the same as example 2 except that in this example the KH570 coupling agent is replaced by a gamma-glycidoxypropyl trimethoxysilane (A-187) coupling agent.
Example 5
This example is substantially the same as example 1, except that in this example, an inorganic electrolyte Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) substitution to Li 0.5 La 0.5 TiO 3 。
Example 6
This example is substantially the same as example 1 except that the mass of the positive electrode active material NCM811 in this example is 24g, and the mass of the inorganic electrolyte particle LLZTO is 16g.
Example 7
This example is substantially the same as example 1 except that the mass of the positive electrode active material NCM811 in this example is 32g, and the mass of the inorganic electrolyte particle LLZTO is 8g.
Example 8
This example is substantially the same as example 1 except that the concentration of the powder material in this example is 0.5g/mL.
Example 9
This example is substantially the same as example 1 except that the concentration of the powder material in this example is 1.2g/mL.
Example 10
This example is substantially identical to example 1, except that the mass fraction of KH570 coupling agent in the intermediate solution in this example is 13%.
Example 11
This example is substantially identical to example 1, except that the mass fraction of KH570 coupling agent in the intermediate solution in this example is 25%.
Example 12
This example is substantially the same as example 1 except that the mass of the positive electrode active material NCM811 in this example was 34.65g, the mass of the inorganic electrolyte particles LLZTO was 0.35g, and the mass of the KH570 coupling agent was 15g.
Example 13
This example is substantially the same as example 1 except that the mass of the positive electrode active material NCM811 in this example is 49.45g, the mass of the inorganic electrolyte particles LLZTO is 0.5g, and the mass of the KH570 coupling agent is 0.05g.
Comparative example 1
This comparative example is substantially the same as example 1 except that no coupling agent is added to the composite positive electrode material in this example.
Comparative example 2
This comparative example is substantially the same as example 1 except that the coupling agent in the composite positive electrode material in this example is a silane coupling agent.
Transmission electron microscopy was performed on the composite cathode material of example 1 to obtain a TEM image of the composite cathode material, and the result is shown in fig. 2.
As can be seen from FIG. 2, KH570 coupling agent is coated on the surface of the inorganic solid electrolyte, and the thickness of the coating layer is 5nm.
Battery example 1
The embodiment of the battery provides a button cell, and the preparation method comprises the following steps:
29.16g of the composite positive electrode material of the example 1, 6g of polyvinylidene fluoride (PVDF) glue solution with the mass fraction of 5%, 0.39g of super pl conductive carbon black and 0.15g of conductive graphite KS-6 are weighed, ball milling is carried out for 2 hours at the speed of 300r/min to obtain positive electrode slurry, the positive electrode slurry is coated, then baked for 2 hours by using a 60 ℃ baking oven, and then transferred to a vacuum baking oven with the vacuum degree of less than or equal to 133Pa, and dried for 12 hours at 120 ℃ to obtain a positive electrode plate; wherein the mass ratio of the positive electrode material to the super pl conductive carbon black to the conductive graphite KS-6 to the binder PVDF is 97.2:1:1.3:0.5;
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 13
Battery examples 2 to 13 were substantially the same as battery example 1, except that the composite cathode materials of examples 2 to 13 were used instead of the composite cathode material of battery example 1.
Comparative examples 1 to 2
Battery comparative examples 1 to 2 were substantially the same as battery example 1, except that the composite cathode material of battery example 1 was replaced with the composite cathode material of comparative examples 1 to 2.
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. 3.
As can be seen from fig. 3, KH570 coating treatment on SEM image modified NCM811 electrode components were uniformly distributed, and KH570 introduction did not affect the mixing distribution of positive electrode components.
The charge and discharge performance of the battery example 1 was tested by a new charge and discharge test system with a test voltage range of 2.7V to 4.2V, the results of which are shown in fig. 4.
As can be seen from fig. 4, the composite positive electrode material modified by KH570 has good cycle performance under 0.5C current.
The composite positive electrode material, 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 illustrate the principle and the implementation of the application, and the description of the above 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 (13)
1. The preparation method of the composite positive electrode material is characterized by comprising the following steps:
mixing a positive electrode active material with inorganic electrolyte particles to obtain a powder material, wherein the inorganic electrolyte particles comprise oxide solid electrolyte;
dispersing the powder material in a first solvent to obtain a dispersion liquid;
mixing an alcohol aqueous solution and a coupling agent to obtain an intermediate solution, wherein the coupling agent is a coupling agent capable of generating hydroxyl by hydrolysis, and the coupling agent capable of generating hydroxyl by hydrolysis comprises at least one of a vinyl silane coupling agent and an epoxy silane coupling agent;
and mixing the dispersion liquid and the intermediate solution for reaction to obtain the composite positive electrode material.
2. The method for preparing a composite positive electrode material according to claim 1, wherein,
the positive electrode active material comprises at least one of lithium cobaltate, lithium nickel manganate, lithium iron phosphate and lithium nickel cobalt manganate; and/or
The average particle diameter D50 of the positive electrode active material is 0.5-100 mu m; and/or
The average particle diameter D50 of the inorganic electrolyte particles is 10-1000 nm; and/or
The first solvent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The alcohol substance in the alcohol water solution comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The intermediate solution comprises a silane coupling agent and silanol.
3. The method for preparing a composite positive electrode material according to claim 2, wherein,
the mass ratio of the inorganic electrolyte particles to the positive electrode active material is (0.1 to 40): (60-99.9); and/or
The mass ratio of the powder material to the coupling agent is (70-99.9): (0.1-30); and/or
In the dispersion liquid, the mass concentration of the powder material is 0.1-2 g/mL; and/or
In the alcohol water solution, the mass concentration of the alcohol substances is 95% -99%; and/or
The mass fraction of the coupling agent in the intermediate solution is 5% -25%.
4. The method for preparing a composite positive electrode material according to claim 1, wherein,
after the positive electrode active material and the inorganic electrolyte particles are mixed, the method further comprises the step of performing first ball milling treatment, wherein the ball milling rate of the first ball milling treatment is 300-350 r/min, and the ball milling time of the ball milling treatment is 0.5-1 h; and/or
The dispersing method comprises ultrasonic dispersing, wherein the frequency of the ultrasonic dispersing is 30-50 kHz, and the time of the ultrasonic dispersing is 20-40 min; and/or
The mixing method is that the first stirring is carried out, the speed of the first stirring is 400-1200 r/min, and the time of the first stirring is 5-20 min; and/or
The second stirring is carried out after the dispersion liquid and the intermediate solution are mixed, the speed of the second stirring is 400-1200 r/min, the time of the second stirring is 2-6 h, and the second stirring is carried out at the temperature of 30-80 ℃.
5. The method for preparing a composite positive electrode material according to claim 4, wherein,
after the second stirring, performing centrifugal separation washing and vacuum drying by using a detergent to obtain a composite anode material;
wherein the detergent comprises at least one of ethanol, methanol, propylene glycol, glycerol, ethylene glycol, amyl alcohol, hexanol, n-butanol and isopropanol; and/or
The centrifugal separation speed is 5000-8000 r/min, and the centrifugal separation time is 3-5 min; and/or
The temperature of the vacuum drying is 30-200 ℃; the time of vacuum drying is 1-48 h.
6. A composite positive electrode material prepared by the preparation method of any one of claims 1 to 5, wherein the composite positive electrode material comprises inorganic electrolyte particles modified by a coupling agent and a positive electrode active material, the inorganic electrolyte particles comprise oxide solid electrolyte, the coupling agent is a coupling agent capable of generating hydroxyl through hydrolysis, and the coupling agent capable of generating hydroxyl through hydrolysis comprises at least one of a vinyl silane coupling agent and an epoxy silane coupling agent.
7. The composite positive electrode material according to claim 6, wherein,
the positive electrode active material comprises at least one of lithium cobaltate, lithium nickel manganate, lithium iron phosphate and lithium nickel cobalt manganate; and/or
The average particle diameter D50 of the positive electrode active material is 0.5-100 mu m; and/or
The average particle diameter D50 of the inorganic electrolyte particles is 10-1000 nm.
8. The composite positive electrode material according to claim 6, wherein,
the mass ratio of the inorganic electrolyte particles to the positive electrode active material is (0.1 to 40): (60-99.9); and/or
The mass ratio of the mass sum of the inorganic electrolyte particles and the positive electrode active material to the coupling agent is (70 to 99.9): (0.1-30).
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises a conductive material, a binder and the composite positive electrode material produced by the production method according to any one of claims 1 to 5, or the composite positive electrode material according to any one of claims 6 to 8.
10. The positive electrode sheet of claim 9, wherein the conductive material comprises at least one of conductive carbon black, conductive graphite, acetylene black, carbon nanotubes, carbon nanofibers, ketjen black; and/or
The binder comprises at least one of polyvinylidene fluoride, polyacrylonitrile, styrene-butadiene latex, polyimide, hydroxymethyl cellulose, polytetrafluoroethylene emulsion, polyacrylate, hydrogenated nitrile rubber and polyurethane.
11. The positive electrode sheet according to claim 9, wherein in the positive electrode sheet, the mass ratio of the composite positive electrode material, the conductive material, and the binder is (80 to 97.2): (2.3-10): (0.5-10).
12. A solid-state battery comprising a negative electrode tab, a solid-state electrolyte, and a positive electrode tab according to any one of claims 9 to 11.
13. The solid state battery of claim 12, wherein the negative electrode tab comprises at least one of a graphite negative electrode, a metallic lithium negative electrode, a silicon-based negative electrode, a silicon-graphite composite negative electrode, a metallic lithium alloy negative electrode, a copper foil lithium-free negative electrode; and/or
The solid electrolyte includes at least one of a sulfide electrolyte, an oxide electrolyte, a halide electrolyte, a polymer electrolyte, or a composite electrolyte.
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