CN116936750A - Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery - Google Patents

Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery Download PDF

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Publication number
CN116936750A
CN116936750A CN202311199688.6A CN202311199688A CN116936750A CN 116936750 A CN116936750 A CN 116936750A CN 202311199688 A CN202311199688 A CN 202311199688A CN 116936750 A CN116936750 A CN 116936750A
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China
Prior art keywords
lithium ion
ion battery
negative plate
negative electrode
shaping
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CN202311199688.6A
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张成智
谭军
王飞
薛凌霄
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Ji Hua Laboratory
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Ji Hua Laboratory
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative 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

Abstract

The application discloses a lithium ion battery negative plate and a preparation method thereof, negative plate slurry and a lithium ion battery, and belongs to the field of lithium ion batteries. The preparation method of the lithium ion battery negative plate comprises the following steps: coating the active material with the surface oxide removed by using an organic material to obtain a modified active material; heating and shaping the modified active substance to obtain a shaped modified active substance; mixing the shaping modified active substance and a film forming agent to obtain negative plate slurry, and coating the negative plate slurry on the surface of a current collector to obtain an initial negative plate; and carbonizing the initial negative plate to obtain the lithium ion battery negative plate. The lithium ion battery negative plate provided by the application has a stable and uniform carbon coating layer, has good electron and ion transmission properties, can enable the lithium ion battery to obtain high first coulomb efficiency, and has excellent cycle, multiplying power and low-temperature performance.

Description

Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery
Technical Field
The application relates to the field of lithium ion batteries, in particular to a lithium ion battery negative plate, a preparation method thereof, negative plate slurry and a lithium ion battery.
Background
In the face of the increasing portable electronic equipment and electric automobile markets, lithium ion battery energy storage will occupy more and more share in the future energy storage market, which has a significant impact on the technology of developing lithium ion batteries with higher energy density. Wherein the performance and preparation process of the battery composition material basically determine the comprehensive performance of the battery. The optimization of pole piece preparation has particular advantages over materials, which determine the performance of the active substance, especially in the preparation of thick pole pieces.
The pole piece design comprises optimization of current collector, conductive agent, binder and the like, and structural designs of flexible electrode, self-support and the like. Wherein the optimization of the current collector is mainly focused on: first, the current collector is thinned, and the proportion of inactive substances is reduced. Secondly, the microstructure is designed on the current collector, so that the connection to active substances and the like is enhanced. The optimization of the two current collectors has the problems of high manufacturing cost, complex process and the like. The main purpose of the conductive agent optimization is to improve the electron and ion transmission property of the pole piece, and the conductive agent with better effect is graphene and carbon nano tube at present, but is limited by cost and complexity of pole piece preparation. The structural designs of the flexible electrode, the self-supporting electrode and the like can obtain excellent electrochemical performance in the button cell, particularly in terms of surface capacity, the ultra-high energy density is reflected, but the problems that the flexible electrode is difficult to weld the electrode lugs and the like restrict the practical application of the flexible electrode. Compared with the optimization of the first two pole pieces and the design of the flexible electrode, the design of a proper adhesive is the most promising optimization scheme. The binder having excellent electron and ion transport properties not only serves as a binder but also allows no conductive agent to be used in the electrode sheet, and thus increases the duty ratio of active materials in the electrode sheet, thereby improving the energy density of the battery. However, the production cost of the currently reported adhesive is high, the process is complex, and the large-scale application of the adhesive is restricted, so that a new pole piece preparation process is necessary to be explored to replace the conductive adhesive.
Therefore, development of a new pole piece preparation process and a pole piece are needed to improve the comprehensive performance of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems of the background art, the application provides a lithium ion battery negative plate, a preparation method thereof, negative plate slurry and a lithium ion battery.
In order to achieve the above purpose, the application provides a preparation method of a lithium ion battery negative plate, comprising the following steps:
coating the active material with the surface oxide removed by using an organic material to obtain a modified active material;
heating and shaping the modified active substance to obtain a shaped modified active substance;
mixing the shaping modified active substance and a film forming agent to obtain negative plate slurry, and coating the negative plate slurry on the surface of a current collector to obtain an initial negative plate;
and carbonizing the initial negative plate to obtain the lithium ion battery negative plate.
In some embodiments of the application, the oxide is removed by etching the active material with an acidic or basic material.
In some embodiments of the application, the acidic substance comprises at least one of hydrogen fluoride, sulfuric acid, hydrochloric acid;
and/or the alkaline substance comprises at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
In some embodiments of the application, the organic material comprises dopamine, dopamine hydrochloride, phenolic resin, epoxy resin, acrylamide, ethyleneimine, maleic anhydride, natural vegetable gum, ethylene oxide, aqueous asphalt emulsion, polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-setting resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastic, polyphenylene sulfide, polyetherketoneketone, polyaryletherketone, polyurethane elastomer, polyphenylene sulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyetheretherketone, polyacrylic acid, lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethylcellulose, hydroxyethyl cellulose, polyacrylamide, polyethyleneimine, polymaleic anhydride, polyquaternary amine salts, hydrolyzed polyacrylamide, polyethylene oxide, ionic water-soluble epoxy resin, ionic maleic anhydride polybutadiene resin, cationic water-soluble polychlorinated resin, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polystyrene sulfonate, polydopamine, polyethylene glycol, polyurethane, aqueous chitosan, polyvinyl pyrrolidone, polysaccharide, gum, pullulan, calcium alginate, karaya gum, and their derivatives.
In some embodiments of the application, the active material is a negative electrode material comprising at least one of graphite, hard carbon, a silicon oxygen compound, and silicon.
In some embodiments of the application, the temperature range of the heat setting is 100 ℃ to 1500 ℃;
and/or the heating rate of the heating shaping is (1-10) DEG C/min;
and/or the heat preservation time of the heating shaping is 1-24 h;
and/or the carbonization temperature ranges from 250 ℃ to 1500 ℃;
and/or the carbonization temperature rising rate is (1-10) DEG C/min;
and/or the carbonization heat preservation time is 1-24 h.
In some embodiments of the application, the styling modificationParticle size distribution D of active substance 50 In the range of 1 μm to 30 μm;
and/or the compaction density of the lithium ion battery negative plate is 1. g cm -3 ≤ρ≤5.0 g·cm -3 ；
And/or the single-sided surface density of the lithium ion battery negative plate is (1-200) mg cm -2 ；
And/or the thickness of the lithium ion battery negative plate is 20-1000 μm.
In some embodiments of the application, the film former comprises one or more of polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-setting resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastic, polyphenylene sulfide, polyetherketoneketone, polyaryletherketone, polyurethane elastomer, polyphenylene sulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyetheretherketone, polyacrylic acid, lithium polyacrylate, sodium carboxymethylcellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethylcellulose, hydroxyethyl cellulose, polyacrylamide, polyethyleneimine, polymaleic anhydride, polyquaternium, hydrolyzed polyacrylamide, natural plant gum, polyethylene oxide, ionic water-soluble epoxy resin, ionic maleated polybutadiene resin, cationic water-soluble polychlorinated resin, aqueous asphalt emulsion, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polystyrene sulfonate, polydopamine, polyethylene glycol, aqueous polyurethane, guar gum, chitosan, gelatin, polyvinylpyrrolidone, xanthan gum, calcium alginate, karaya gum, and gum arabic and derivatives thereof.
In some embodiments of the application, the negative electrode sheet slurry has a viscosity in the range of 1000 mPa-s to 8000 mPa-s.
In order to achieve the above object, the present application also provides a negative electrode sheet slurry comprising a modified active material, wherein the active material from which the oxide on the surface is removed is coated with an organic material, and then subjected to heat setting to obtain the set modified active material.
In order to achieve the above purpose, the application also provides a lithium ion battery, which comprises the lithium ion battery negative electrode sheet or the negative electrode sheet slurry.
The application has the beneficial effects that:
(1) The active material is subjected to surface modification, and the surface is free of oxide, so that the volume change of the active material in the cycling process of the lithium ion battery is more limited, and the expansion of the pole piece can be prevented; in addition, the surface of the active material is coated with organic substances, and a thin carbon layer is formed on the surface through heating and shaping, so that the lithium ion battery has excellent electron and ion transmission properties, and can obtain higher first coulomb efficiency and long-cycle stability.
(2) The lithium ion negative electrode sheet disclosed by the application does not contain organic matters after carbonization, is low in water content, and has the advantages of high heat conduction and non-inflammability; in addition, the lithium ion negative electrode plate does not contain conductive agent, so that the proportion of low/inactive substances in the electrode is reduced, the process complexity and the manufacturing cost are reduced, the high-compaction electrode plate is easy to prepare, and the energy density of the lithium ion battery is improved; in addition, after carbonization, the negative plate has a stable and uniform carbon coating layer, a bonding effect can be formed between the carbon coating layer and an active substance and between the carbon coating layer and a current collector, a better bonding effect can be obtained without adding a binder, the carbon coating layer also plays a role of a conductive agent, the negative plate has excellent electron and ion transmission performance without adding the conductive agent, an ultra-thick plate (the thickness of the plate is more than 300 mu m) can be designed, and the proportion of inactive components can be further reduced, so that the energy density of a battery can be improved, and the cost can be reduced.
(3) The lithium ion battery with the lithium ion negative plate can obtain higher first coulombic efficiency and has excellent cycle, multiplying power and low-temperature performance.
(4) The electrode preparation method disclosed by the application is simple and feasible, can use the water-based film forming agent, uses water as a solvent, has no pollution, is safe and reliable, has low cost, is more universal in applicability and higher in production efficiency, and can realize industrialized mass production.
Drawings
For a clearer description of embodiments of the application or of solutions in the prior art, the following brief description of the drawings is given for the purpose of illustrating the embodiments or the solutions in the prior art, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained from the structures shown in these drawings without the need for inventive effort for a person skilled in the art.
FIG. 1 is an explanatory view of the method for producing an electrode according to example 1 of the present application.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the electrode produced in example 1 of the present application.
FIG. 3 is a focused ion beam microscope (FIB-SEM) of the electrode prepared in example 1 of the present application.
FIG. 4 is a graph showing the first coulombic efficiency results of the electrode prepared in example 1 of the present application.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
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 embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The description as it relates to "first", "second", etc. in the present application is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present application.
The application provides a preparation method of a lithium ion battery negative plate, which comprises the following steps:
step S10: coating the active material with the surface oxide removed by using an organic material to obtain a modified active material;
step S20: heating and shaping the modified active substance to obtain a shaped modified active substance;
step S30: mixing the shaping modified active substance and a film forming agent to obtain negative plate slurry, and coating the negative plate slurry on the surface of a current collector to obtain an initial negative plate;
step S40: and carbonizing the initial negative plate to obtain the lithium ion battery negative plate.
The negative plate of the lithium ion battery generally contains a current collector, a film forming agent, a conductive agent and an adhesive, and the negative plate is designed and improved to form a carbon coating layer, and the carbon coating layer uniformly coats all contact surfaces of the electrode, so that circulating surface contact is formed between active substances and the current collector, and the current collector is not in a traditional point contact mode. The carbon coating layer can be used as an adhesive and a conductive agent of the negative plate at the same time, and can also be used as a protective layer to limit the volume expansion of the negative plate in the cycle process of the lithium ion battery, and stronger chemical bonding action exists between the carbon coating layer and active material particles and between the carbon coating layer and a current collector, so that the carbon coating layer can adapt to the volume change of active materials, the carbon coating layer is prevented from being broken and the active material particles are prevented from being pulverized, and the formed conductive environment is not easy to be damaged.
In addition, the active material is modified and shaped to form the shaped modified active material which has no oxide on the surface and is coated by the organic material, so that the volume change of the active material in the cycling process of the lithium ion battery can be further limited, the expansion of the pole piece is prevented, and a thin carbon layer is formed on the surface by heating and shaping, and the thin carbon layer has excellent electron and ion transmissibility, so that the lithium ion battery can obtain higher first coulomb efficiency and long-cycle stability. In addition, the application prepares the thin carbon layer on the surface of the active substance, and then obtains the carbon coating layer through carbonization, the thin carbon layer and the carbon coating layer have stronger binding force, and the carbon coating layer can be promoted to uniformly coat between all contact surfaces of the electrode, so that the active substance and the current collector form circular surface contact instead of the traditional point contact mode.
The present application is not limited to a method of removing the oxide on the surface of the active material, and in some embodiments, the active material may be etched with an acidic or basic material to remove the oxide on the surface.
Specifically, an acidic solution or an alkaline solution can be added into the polytetrafluoroethylene lining, then the active substances are added, mixed and stirred for 2-4 hours, taken out, washed to be neutral by deionized water, and then the active substances with surface oxides removed are obtained through centrifugal drying and collection.
The present application is not limited to the types of the acidic substance and the basic substance.
In some embodiments, the acidic species comprises at least one of HF, sulfuric acid, hydrochloric acid. For example, the active material can be etched by HF to remove the oxide on the surface, so that the active material can be prevented from expanding in the cycling process of the lithium ion battery due to the existence of the oxide on the surface of the active material, and the service life of the lithium ion battery is prevented from being influenced.
In some embodiments, the alkaline substance comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide.
The application does not limit the types of organic substances for coating the active substances, in some embodiments, the organic substances are small molecular organic substances, continuous polymerization of the small molecular organic substances is beneficial to realizing uniform coating of the active substances, and after heating and shaping, a thin carbon layer can be formed on the surface of the active substances, so that the volume change of the active substances in the battery cycle process is limited.
In some embodiments, the organic material comprises dopamine, dopamine hydrochloride, phenolic resin, epoxy resin, aqueous epoxy resin, acrylamide, ethyleneimine, maleic anhydride, natural vegetable gums, ethylene oxide, aqueous asphalt emulsion, polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-setting resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastic, polyphenylene sulfide, polyetheretherketone, polyaryletherketone, polyurethane elastomer rubber, polyphenylene sulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyetheretherketone, polyacrylic acid, lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethylcellulose, hydroxyethyl cellulose, polyacrylamide, polyethyleneimine, polymaleic anhydride, polyquaternary amine salts, hydrolyzed polyacrylamide, natural vegetable gums, polyethylene oxide, ionic water-soluble epoxy resin, ionic maleated polybutadiene resin, cationic water-soluble polychlorinated resin, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polystyrene sulfonate, polydopamine, polyethylene glycol, polyurethane, aqueous poly (vinyl pyrrolidone), polysaccharide, gum arabic, gelatin, calcium arabinoxylate, and their derivatives. The organic substances are coated on the surface of the active substances, and after heating and shaping, a stable and firm thin carbon layer can be formed, so that the volume change of the active substances in the battery circulation process is limited.
The engineering plastic comprises a graft copolymer of acrylic rubber, acrylonitrile and styrene.
In some embodiments, the active material is a negative electrode material including at least one of graphite, hard carbon, a silicon oxygen compound, and silicon. After carbonization, the initial negative plate can form a carbon coating layer which wraps active substances, and when the active substances are graphite, the active substances can form a C-O-C bonding effect with the carbon coating layer; when the active substance is hard carbon, the active substance can form a C-N bonding effect with the carbon coating layer; when the active substance is silicon oxide, the active substance can form a bonding effect of C-O-Si with the carbon coating layer; when the active material is silicon, it can form a C-Si bond with the carbon coating. The carbon coating layer and the active material form a bonding effect, and a bonding effect is formed between the current collector, so that the active material can be firmly fixed on the surface of the current collector, and even in the long-cycle process of the battery, the active material is not easy to expand or crack due to pulverization.
The present application is not limited to the temperature of the heat setting, and in some embodiments, the temperature of the heat setting is in the range of 100 ℃ to 500 ℃, for example, the temperature of the heat setting may be any one of the temperature values of 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, etc. the present application can complete the setting treatment of the active material at a lower temperature to obtain the active material with a firm thin carbon layer formed on the surface, so that the volume change is limited in the battery cycle process, and excellent electron and ion transmissibility can be obtained, and the lithium ion battery can obtain higher first coulomb efficiency and long cycle stability.
The application does not limit the heating rate of the heating shaping, in some embodiments, the heating rate of the heating shaping is 1-10 ℃/min, and the heating shaping is carried out by a slow heating mode, which is beneficial to forming a uniform and firm thin carbon layer on the surface of the active substance, and excellent electron and ion transmission performance is obtained.
The application does not limit the heat preservation time of the heat setting, in some embodiments, the heat preservation time of the heat setting is 1 h-24 h, and the heat preservation treatment is beneficial to obtaining active substances which form a uniform and firm thin carbon layer on the surface, thereby obtaining excellent electron and ion transmission.
It can be understood that the above limitation on the heating temperature, the heating rate and the heat preservation time of the heating shaping can only satisfy one of them, or can also satisfy both, and simultaneously satisfies the active material which is favorable for obtaining a uniform and firm thin carbon layer on the surface, so that the volume change of the active material in the process of battery circulation is limited.
The application is not limited to carbonization temperatures, and in some embodiments, carbonization temperatures range from 250 ℃ to 1500 ℃.
The application is not limited to the rate of carbonization, and in some embodiments, the rate of carbonization is 1-h deg.C/min to 10 deg.C/min.
The application is not limited to the soak time of carbonization, and in some embodiments, the soak time of carbonization is 1 h to 24 h.
The application constructs an active substance/carbon composite structure on the negative plate by carbonizing the negative plate, namely, the active substance is wrapped by a carbon coating layer, so as to prepare the negative plate which does not contain organic matters and can be used as the binder and the conductive agent simultaneously. The carbon coating layer and the active material particles and the carbon coating layer and the current collector have strong chemical bonding effect, so that the carbon coating layer can adapt to the volume change of the active material, the carbon coating layer is prevented from being broken and the active material particles are prevented from being pulverized, and the formed conductive environment is not easy to be damaged. In addition, the carbon coating layer uniformly coats between the contact surfaces of the electrodes, so that a circulating surface contact between the active material and the current collector can be formed, instead of the conventional point contact mode. Furthermore, the carbon coating layer can also be used as a protective layer to limit the volume expansion of the negative plate in the cycling process of the lithium ion battery, so that the mechanical stability and the electrochemical stability of the negative plate are improved.
It can be understood that the above restrictions on the carbonization temperature, the heating rate and the heat preservation time can be satisfied only by one of them, or can be satisfied simultaneously, and simultaneously, the negative electrode sheet favorable for obtaining a uniform and firm carbon coating layer on the surface is satisfied, so that the volume change of the active material in the process of battery circulation is limited.
In some embodiments, the particle size distribution D of the styling modification active 50 In the range of 1 μm to 30 μm, e.g. particle size distribution D 50 Can be any one of 1 μm, 2 μm, 5 μm, 8 μm, 9 μm, 10 μm, 11 μm, 13 μm, 15 μm, 18 μm, 19 μm, 20 μm, 21 μm, 24 μm, 25 μm, 27 μm, 29 μm, 30 μm, etc. in the range of 1 μm to 30 μmThe sizing modified active substance has better dispersibility in the particle size range, and can be uniformly mixed with the film forming agent to prepare the uniform and flat lithium ion battery negative plate.
In some embodiments, the modified active material may be heated to form a shaped modified active material having a pore structure that facilitates ion and electron transport properties.
In some embodiments, the carbonization treatment of step S40 may be performed in at least one atmosphere of nitrogen, argon, and argon-hydrogen mixture.
In some embodiments, the lithium ion battery negative plate of the application has a compacted density of 1.0g cm -3 ≤ρ≤5.0 g·cm -3 。
In some embodiments, the single-sided surface density of the lithium ion battery negative plate is 1-200 mg cm -2 。
The thickness of the lithium ion battery negative plate is not limited, and the thickness can be limited according to the design requirement of the lithium ion battery. In some embodiments, the thickness of the lithium ion battery negative electrode sheet is 20-1000 μm, for example, the thickness may be 20 μm, 30 μm, 40 μm, 80 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 950 μm, 1000 μm. In the embodiment, because the carbon coating layer of the lithium ion battery negative electrode plate has excellent electron and ion transmission property, and the active substance is not easy to expand, the thickness of the lithium ion battery negative electrode plate can be designed to be more than or equal to 300 mu m, the proportion of inactive components is further reduced, and therefore the energy density of the lithium ion battery can be further improved, and the cost is reduced.
The application is not limited in the types of film forming agents, in some embodiments, the film forming agents are aqueous film forming agents, the aqueous film forming agents are soluble in water, and water can be used as a solvent, so that the application is safe, reliable, pollution-free, low in cost, more general in applicability, higher in production efficiency and beneficial to realizing industrial mass production.
In some embodiments, the film forming agent comprises one or more of polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-setting resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastic, polyphenylene sulfide, polyetheretherketone, polyaryletherketone, polyurethane elastomer, polyphenylene sulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyetheretherketone, polyacrylic acid, lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyethylenimine, polymaleic anhydride, polyquaternium, hydrolyzed polyacrylamide, natural plant gum, polyethylene oxide, ionic water-soluble epoxy resin, ionic maleic polybutadiene resin, cationic water-soluble polychlorinated resin, aqueous asphalt emulsion, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polystyrene sulfonate, polydopamine, polyethylene glycol, aqueous polyurethane, guar gum, chitosan, gelatin, polyvinylpyrrolidone, xanthan gum, calcium alginate, gellan gum, cyclohexane gum, karaya gum, and gum arabic and its derivatives. The film forming agent has good film forming effect, is water-soluble, can be dissolved by taking water as a solvent, is safe, reliable and pollution-free, has low cost, is more universal in applicability, has higher production efficiency, and is favorable for realizing industrialized mass production.
The engineering plastic comprises a graft copolymer of acrylic rubber, acrylonitrile and styrene.
In some embodiments, the viscosity of the negative electrode sheet slurry ranges from 1000 to 8000mpa·s, for example, the viscosity of the slurry may be any one of 1000mpa·s, 2000mpa·s, 3000mpa·s, 4000mpa·s, 5000mpa·s, 6000mpa·s, 7000mpa·s, 8000mpa·s, and the like, and the negative electrode sheet slurry having the above viscosity ranges is coated on the surface of the current collector, so that higher adhesive force may be provided, and the negative electrode sheet is not prone to pulverization cracking during the cycle of the lithium ion battery.
The present application is not limited to the type of current collector, and in some embodiments, the current collector includes copper foil, aluminum foil, or the like. When the current collector is copper foil, the carbon coating layer wrapping the active substance is formed after the initial negative plate is carbonized, and a bonding effect is formed among the active substance, the carbon coating layer and the copper foil current collector, so that the active substance can be firmly fixed on the surface of the current collector, and even in the long-cycle process of a battery, the active substance is not easy to expand or generate a chalking cracking phenomenon.
The application also provides a negative electrode plate slurry, which comprises a shaping modified active substance, wherein the active substance with the surface oxide removed is coated by an organic substance, and then the shaping modified active substance is obtained by heating and shaping. The specific preparation method can refer to the preparation of the negative plate slurry in the preparation method of the negative plate of the lithium ion battery. In the embodiment, the active material is modified, the surface is free of oxide and coated by the organic material, so that the volume change of the active material in the cycling process of the lithium ion battery is more limited, and the expansion of the negative electrode plate can be prevented; in addition, the active material can form a thin carbon layer on the surface after modification treatment and shaping, has excellent electron and ion transmission, is used for preparing a negative plate and applied to a lithium ion battery, and can improve the electrochemical performance and the service life of the lithium ion battery.
In some embodiments, the negative electrode sheet slurry further comprises a film-forming material, which can be obtained by uniformly mixing the film-forming material with the above-described styling-modifying active.
The application also provides a lithium ion battery, which comprises the lithium ion battery negative plate, and the lithium ion battery at least has all the beneficial effects with the lithium ion negative plate and is not repeated herein.
In some embodiments, the lithium ion battery comprises the negative electrode plate slurry, and the negative electrode plate slurry is used for preparing a lithium ion negative electrode plate, so that the volume change of an active substance in the cycling process of the lithium ion battery is more limited, and the expansion of the negative electrode plate can be prevented; in addition, the active material can form a thin carbon layer on the surface after modification treatment and shaping, has excellent electron and ion transmission, is used for preparing a negative plate and applied to a lithium ion battery, and can improve the electrochemical performance and the service life of the lithium ion battery.
The technical scheme of the present application will be further described in detail with reference to the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
Referring to fig. 1, the preparation method of the lithium ion battery negative plate of the embodiment includes the following steps:
step S10: sucking 18 mL deionized water into a polytetrafluoroethylene lining, adding 2 mL diluted HF (49 wt%), uniformly mixing, adding 2 g silicon powder with the granularity of 5 mu m, continuously stirring in a fume hood for 2h hours, taking out, adding deionized water for cleaning to neutrality, and centrifugally drying and collecting to obtain modified active substance silicon (expressed by p-Si) with a surface oxide layer removed.
Step S20: dissolving 2.724 g Tris (hydroxymethyl) aminomethane (Tris) in 450 mL deionized water, putting into a water bath at 30 ℃ for stirring, slowly dripping 0.9 mL of HCl solution for stirring uniformly, regulating the pH value to 8.0-8.5 to obtain a Tris-HCl buffer, sequentially adding 600 mg p-Si and 200mg dopamine hydrochloride in the step S10 into the Tris-HCl buffer, stirring in a continuous water bath for 24 h, centrifugally drying, collecting, transferring to a tube furnace for low-temperature heat treatment at 300 ℃ for 1 h shaping, and obtaining the shaped modified active substance namely polydopamine derived carbon coated silicon (expressed by p-Si@C).
Step S30: putting 200mg soluble starch into a weighing bottle, adding 2 mL deionized water, stirring at 80 ℃ in an oil bath for 0.5 h, then adding 200mg of p-Si@C, stirring at room temperature for 4-6 hours to obtain negative electrode sheet slurry, uniformly coating the prepared negative electrode sheet slurry on copper foil with the thickness of 9 mu m, and drying to obtain the initial electrode sheet.
Step S40: after the initial pole piece is punched into a button cell pole piece with the diameter of 12 mm, the button cell pole piece is moved to a tube furnace for heat treatment at the temperature of 1 ℃ for min -1 Heating to 500 ℃ and preserving heat for 2h to prepare the lithium ion battery negative plate coated with uniform carbon.
The present embodiment is madeThe prepared micron silicon-based carbon coated negative plate is directly used as a working plate for assembling the button cell. Wherein the mass of the active substance of the pole piece is 1-2 mg cm -2 (active materials include silicon and carbon).
Assembling a button cell: 1.0. 1.0M lithium hexafluorophosphate (LiPF) 6 ) The volume ratio of the solution is 1:1, ethylene Carbonate (EC) and diethyl carbonate (DEC) were added with 2. 2 wt% of ethylene carbonate (VC) and 7.5. 7.5 wt% of fluoroethylene carbonate (FEC) as an electrolyte, and a lithium metal sheet was used as a counter electrode to assemble a button cell.
Performance test 1: the micron silicon-based carbon coated negative plate of example 1 was characterized by a scanning electron microscope, and the result is shown in fig. 2, and the scanning electron microscope image of fig. 2 shows that a layer of starch carbon is uniformly deposited near the micron silicon particles on the carbon coated negative plate.
Performance test 2: and (3) scanning and characterizing the section of the negative plate coated with the micron silicon-based carbon cut by the focused ion beam by using a scanning electron microscope back-scattering electron instrument, wherein a scanning electron microscope back-scattering electron image is shown in fig. 3. As can be seen from fig. 3, the electrode forms a good electron and ion transport network after carbonization.
Performance test 3: the button cell of this example was charged and discharged at a current density of 0.33C, and the test results are shown in table 1 and fig. 4.
As shown in FIG. 4, the first discharge specific capacity of the silicon-based carbon-coated negative electrode sheet of the embodiment is 3774.84 mAh.g -1 The specific charge capacity is 3282.85 mAh.g -1 Its ICE (first coulombic efficiency) is as high as 86.97%. The capacity of the battery is still kept to be approximately 1734.19 mAh.g after 50 circles of current density of 0.33 and 0.33C -1 Is a very high capacity of (a).
Example 2
Steps S10-S20: preparation of styling-modified actives in this example reference was made to the preparation method of example 1 to yield polydopamine-derived carbon-coated silicon (denoted p-si@c).
Step S30: and (3) putting 200mg sodium carboxymethylcellulose into a weighing bottle, adding 2 mL deionized water/alcohol mixed solution, stirring for 0.5 h to disperse, adding 200mg p-Si@C, stirring for 4-6 hours at room temperature to obtain negative electrode sheet slurry, uniformly coating the negative electrode sheet slurry on a copper foil with the thickness of 10 mu m, and drying to obtain the initial electrode sheet.
Step S40: after the initial pole piece punched piece is manufactured into a button cell pole piece with the diameter of 12 mm, the button cell pole piece is moved to a tube furnace for heating carbonization treatment, and the carbonization procedure is as follows: at 1 ℃ for min −1 Heating to 500 ℃ and preserving heat for 2 hours to prepare the lithium ion battery negative plate.
The lithium ion battery negative electrode sheet of the embodiment is a silicon negative electrode sheet, and can be directly used as a working electrode sheet for assembling the button battery. Wherein the mass of active substances in the silicon negative electrode sheet is 1-2 mgh.cm −2 (active materials include silicon and carbon).
Assembling the button cell: the electrolyte used was the same as in example 1, and a metallic lithium sheet was used as the counter electrode.
Performance test 1: at a current density of 0.033C (C =3579 mA ·g −1 ) Charging and discharging are carried out, and the first discharge specific capacity of the silicon negative plate of the embodiment is 3296.41 mAh.g -1 The specific charge capacity is 2802.05 mAh.g -1 The initial coulomb efficiency is up to 85.00%, the current density is 0.33 and C, and the capacity is kept to be approximately 1668.32 mAh.g after 50 circles of circulation -1 The capacity of (2) is shown in Table 1.
Example 3
Step S10: sucking 18 mL deionized water into polytetrafluoroethylene lining, adding 2 mL diluted HF (49 wt%), mixing, adding 2 g silica with granularity of 6 μm, continuously stirring in a fume hood for 2h, taking out, adding deionized water for cleaning to neutrality, centrifuging, drying, and collecting to obtain modified active substance silica (expressed by p-SiO) with surface oxide layer removed.
Step S20: dissolving 2.724 g Tris (hydroxymethyl) aminomethane (Tris) in 450 mL deionized water, putting into a water bath at 30 ℃ for stirring, slowly dripping 0.9 mL of HCl solution for stirring uniformly, regulating the pH value to 8.0-8.5 to obtain a Tris-HCl buffer, sequentially adding 600 mg p-SiO and 200mg acrylamide organic micromolecules in the step S10 into the Tris-HCl buffer, continuously stirring in the water bath for 24 h, centrifugally drying, collecting, transferring to a tube furnace for low-temperature heat treatment at 300 ℃ for 1 h shaping, and obtaining the shaped modified active substance, namely polydopamine derived carbon coated silicon (expressed by SiO@C).
Steps S30-S40: 200mg soluble starch and 600 mg SiO@C are taken, and a uniform carbon-coated lithium ion battery negative electrode sheet is prepared in a slurry mixing, coating and carbonization mode in example 1. Wherein the mass of the active substance of the pole piece is 1-5 mg cm -2 (active materials include silicon and carbon).
The electrolyte used for assembling the button cell was the same as in example 1, and a metallic lithium sheet was used as the counter electrode. The negative electrode sheet of this example was an integrated electrode sheet, and was excellent in rate performance, and when the current density reached 0.5C and 1C (C =1580ma g -1 ) Reversible specific capacities are respectively kept at 1243.9 and 955.7 mAh g -1 The integrated electrode has super strong electron ion transport capacity.
Example 4
Steps S10-S20: this example refers to the preparation of steps S10-S20 of example 1 to obtain a polydopamine derived carbon coated silicon (denoted p-si@c).
Steps S30-S40: 200mg soluble starch, 300 mg graphite with granularity of 12 mu m and 300 mg p-Si@C are taken, and a uniform carbon-coated lithium ion battery negative electrode plate is prepared by the mode of size mixing, coating and carbonization in example 1, wherein the mass of active substances of the electrode plate is 5-10 mg cm -2 (active materials include silicon, graphite and derivatized carbon).
The electrolyte used for assembling the button cell was the same as in example 1, and a metallic lithium sheet was used as the counter electrode. At a current density of 0.01C (C =2000 mA g -1 ) The first discharge capacity of the negative electrode sheet of this example was 13.6 mAh, and the charge capacity was 12.1 mAh (the surface capacity was up to 10.7 mAh cm) -2 ) The initial coulomb efficiency is up to 89.1%, and the capacity is still kept at 4.2 mAh cm after 20 circles of current density of 0.1 and 0.1C -2 Is a very high capacity of (a).
Comparative example 1
The shaped and modified active material p-si@c in example 1 was slurried by a conventional slurry mixing method, but was not carbonized to obtain a negative electrode sheet for a battery, comprising the steps of:
and (3) putting 200mg soluble starch into a weighing bottle, adding 2 mL deionized water, stirring in an oil bath at 80 ℃ for 0.5 h, adding 200mg of p-Si@C, and stirring at room temperature for 4-6 hours to obtain the negative electrode sheet slurry. And uniformly coating the prepared negative plate slurry on a copper foil with the thickness of 9 mu m, and drying to obtain the initial plate.
The battery was assembled using the electrolyte according to example 1, and the test patterns were also identical.
Comparative example 2
Comparative example 2 the active material silicon powder of example 1 was slurried using a conventional slurrying method without modifying and sizing the silicon powder, comprising the steps of: respectively grinding and mixing 192 mg silicon powder with the granularity of 2 g and 24 mg conductive carbon black with the granularity of 5 mu m, adding 400 mg of lithium polyacrylate for size mixing, taking deionized water as a binder solvent, and uniformly coating the adhesive mixture on a copper foil to obtain the working electrode plate. The battery was assembled using the electrolyte according to example 1, and the test patterns were also identical.
TABLE 1
As is clear from examples 1 to 4, the negative electrode slurry of the present application contains a shaped and modified active material, and the negative electrode sheet obtained by carbonization treatment has a high specific capacity for initial discharge, a high specific charging capacity for initial coulomb efficiency, and a high capacity after 50 cycles of 0.33 and C cycles, and has excellent electrochemical properties.
In comparative example 1, the electrochemical performance was reduced and the capacity was only 2.17 mAh.g after 50 cycles of 0.33C cycles without carbonization -1 。
Comparative example 1, in which no modification or setting treatment was performed on the active material, had a capacity of only 0.56 mAh.g after 50 cycles of 0.33C -1 。
The foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the scope of the application, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.

Claims (10)

1. The preparation method of the lithium ion battery negative plate is characterized by comprising the following preparation steps:
coating the active material with the surface oxide removed by using an organic material to obtain a modified active material;
heating and shaping the modified active substance to obtain a shaped modified active substance;
mixing the shaping modified active substance and a film forming agent to obtain negative plate slurry, and coating the negative plate slurry on the surface of a current collector to obtain an initial negative plate;
and carbonizing the initial negative plate to obtain the lithium ion battery negative plate.
2. The method for producing a negative electrode sheet for a lithium ion battery according to claim 1, wherein the oxide is removed by etching the active material with an acidic material or an alkaline material.
3. The method for preparing a negative electrode sheet for a lithium ion battery according to claim 2, wherein the acidic substance comprises at least one of hydrogen fluoride, sulfuric acid, and hydrochloric acid;
and/or the alkaline substance comprises at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
4. The method for preparing a negative electrode sheet for a lithium ion battery according to claim 1, wherein the organic substance comprises dopamine, dopamine hydrochloride, phenolic resin, epoxy resin, acrylamide, ethyleneimine, maleic anhydride, natural vegetable gum, ethylene oxide, aqueous asphalt emulsion, polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-setting resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastic, polyphenylene sulfide, polyetherketoneketone, polyaryletherketone, polyurethane elastomer, polyphenylenesulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyetheretherketone, polyacrylic acid, lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethylcellulose, hydroxyethyl cellulose, polyacrylamide, polyethyleneimine, polymaleic anhydride, polyquaternium salt, hydrolyzed polyacrylamide, polyethylene oxide, ionic water-soluble epoxy resin, ionic water-soluble polychloride resin, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polyethylene sulfonate, sodium polyacrylate, polyurethane, aqueous polysaccharide, sodium alginate, gelatin, calcium alginate, etc.;
and/or the active substance is a negative electrode material, and the negative electrode material comprises at least one of graphite, hard carbon, silicon oxygen compound and silicon.
5. The method for preparing the lithium ion battery negative plate according to claim 1, wherein the temperature range of the heating and shaping is 100-1500 ℃;
and/or the heating rate of the heating shaping is (1-10) DEG C/min;
and/or the heat preservation time of the heating shaping is 1-24 h;
and/or the carbonization temperature ranges from 250 ℃ to 1500 ℃;
and/or the temperature rising rate of carbonization is (1-10) DEG C/min;
and/or the carbonization heat preservation time is 1-24 h.
6. The method for preparing a negative electrode sheet for a lithium ion battery according to claim 1, wherein the particle size distribution D of the shaped modified active material 50 The range is 1-30 mu m;
and/or, theThe compaction density of the lithium ion battery negative plate is 1.0g cm -3 ≤ρ≤5.0 g·cm -3 ；
And/or the single-sided surface density of the lithium ion battery negative plate is (1-200) mg cm -2 ；
And/or the thickness of the lithium ion battery negative plate is 20-1000 μm.
7. The method for preparing the lithium ion battery negative plate according to claim 1, wherein,
the film forming agent comprises one or more of polylactic acid, polytetrafluoroethylene, polyvinylidene fluoride, photo-curing resin, polyetherimide, polyacrylonitrile, nylon, acrylonitrile, polycarbonate, engineering plastics, polyphenylene sulfide, polyether ether ketone, polyaryletherketone, polyurethane elastic rubber, polyphenylene sulfone resin, polysulfone, polyurethane, imide, liquid crystal polymer, polyacrylic acid, lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate, starch derivatives, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyethyleneimine, polymaleic anhydride, polyquaternium, hydrolyzed polyacrylamide, natural vegetable gum, polyethylene oxide, ionic water-soluble epoxy resin, ionic maleic polybutadiene resin, cationic water-soluble polychlorinated resin, aqueous asphalt emulsion, aqueous epoxy resin, aqueous polyacrylate, sodium carboxymethyl starch, polyvinyl alcohol, sodium polystyrene sulfonate, polydopamine, polyethylene glycol, aqueous polyurethane, chitosan, gelatin, polyvinylpyrrolidone, calcium alginate, gellan gum, cyclodextrin, karaya gum, and derivatives thereof.
8. A lithium ion battery negative electrode sheet prepared by the method for preparing a lithium ion battery negative electrode sheet according to any one of claims 1 to 7.
9. The negative electrode sheet slurry is characterized by comprising a shaping modification active substance, wherein the active substance with surface oxides removed is coated with an organic substance, and then the shaping modification active substance is obtained by heating and shaping.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery negative electrode sheet according to claim 8 or the negative electrode sheet slurry according to claim 9.
CN202311199688.6A 2023-09-18 2023-09-18 Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery Pending CN116936750A (en)

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