CN113871574A - Lithium ion battery negative plate and preparation method and application thereof - Google Patents

Lithium ion battery negative plate and preparation method and application thereof Download PDF

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Publication number
CN113871574A
CN113871574A CN202111120966.5A CN202111120966A CN113871574A CN 113871574 A CN113871574 A CN 113871574A CN 202111120966 A CN202111120966 A CN 202111120966A CN 113871574 A CN113871574 A CN 113871574A
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lithium ion
hard carbon
ion battery
negative electrode
battery negative
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CN113871574B (en
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刘永兴
李若楠
王水良
王彦青
孙化雨
其他发明人请求不公开姓名
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/134—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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 invention relates to a lithium ion battery negative plate and a preparation method and application thereof, wherein the lithium ion battery negative plate comprises the following components in parts by weight: 98-102 parts of binary composite material, 0.5-1.5 parts of conductive agent, 1-3 parts of binder and 0.1-2 parts of lithium supplement material; wherein the binary composite material is a composite material of sheet-shaped porous hard carbon and a nano silicon-based material. According to the invention, the sheet-shaped porous hard carbon is compounded with the nano silicon-based material, so that the prepared lithium ion battery negative plate has the quick charge capability and the low expansion performance of the hard carbon material and the high capacity of the nano silicon-based material. Meanwhile, the defects of hard carbon and silicon-based materials are overcome by supplementing lithium through the negative electrode, and the first coulombic efficiency is improved.

Description

Lithium ion battery negative plate and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, relates to a negative electrode material, and particularly relates to a lithium ion battery negative electrode plate and a preparation method and application thereof.
Background
At present, the negative electrode material is mainly a graphite-based material, but the graphite negative electrode material has the problems of low capacity and poor rate performance, and ultra-long endurance and ultra-fast charge are key development directions of next-generation lithium ion batteries. Pure graphite materials cannot meet the requirements, and a negative electrode material with higher energy density and better quick charging performance needs to be developed. Except graphite materials, the hard carbon material is a novel negative electrode material, and has the advantages of high capacity, good kinetics and low expansion compared with the graphite material, but the first coulombic efficiency is low; the silicon-based material is also considered as a relatively promising negative electrode material, and has higher capacity, but the first coulombic efficiency is lower, and the rate performance is poorer.
In the prior art, the energy density and the quick charge performance are both considered generally by adopting a graphite/silicon-based material compounding mode, but the quick charge performance of the graphite basically reaches the limit, and the space for continuously improving the performance is not large. Meanwhile, the silicon-based material and the graphite material have large expansion, so that the structural stability of the battery cell is easily damaged in the cyclic charge and discharge process, and the cyclic attenuation is fast.
Therefore, how to break through the limitation of the traditional graphite material and prepare the lithium ion battery negative plate with the novel negative material, the lithium ion battery negative plate has the advantages of taking account of the quick charging capacity and the low expansion capacity of the hard carbon material and the high capacity performance of the silicon-based material, and simultaneously has high first coulombic efficiency, and the lithium ion battery negative plate is a problem to be solved urgently in the technical field of lithium ion batteries.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a lithium ion battery negative plate, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium ion battery negative electrode sheet, which comprises, by weight:
Figure BDA0003277134210000021
the binary composite material is a composite material of flaky porous hard carbon and a nano silicon-based material.
The hard carbon material has the advantages of high capacity and good dynamic performance, but has the defect of low first coulombic efficiency, and the silicon material is a negative electrode material with higher capacity, but has high expansion rate and poor rate capability, and has low first coulombic efficiency. The lithium ion battery negative plate is prepared by compounding the hard carbon and the silicon material, not only the advantages of the two materials are considered, but also the defects of the two materials are improved. Meanwhile, the low first coulombic efficiency of the hard carbon and silicon materials can be improved by adding the lithium supplement material.
The weight part of the binary composite material in the lithium ion battery negative plate is 98-102 parts, such as 98 parts, 99 parts, 100 parts, 101 parts or 102 parts, but the binary composite material is not limited to the recited values, and other values in the numerical range which are not recited are also applicable.
The weight part of the conductive agent in the lithium ion battery negative plate is 0.5-1.5 parts, for example, 0.5 part, 0.7 part, 1 part, 1.2 parts or 1.5 parts, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The weight part of the binder in the lithium ion battery negative plate is 1-3 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, but the invention is not limited to the recited values, and other values in the numerical range which are not recited are also applicable.
The weight part of the lithium supplement material in the lithium ion battery negative plate is 0.1-2 parts, for example, 0.1 part, 0.5 part, 1 part, 1.5 part or 2 parts, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the mass percentage of the flaky porous hard carbon in the binary composite is 10 to 90 wt%, for example, 10 wt%, 30 wt%, 50 wt%, 70 wt%, or 90 wt%, but not limited to the recited values, and other values not recited in the numerical range are also applicable, and the balance is the nano silicon-based material.
Preferably, the mass percentage of the flaky porous hard carbon in the binary composite is 40 to 80 wt%, for example, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the aspect ratio of the flaky porous hard carbon is 1 (5-100), and may be, for example, 1:5, 1:20, 1:40, 1:80 or 1:100, but is not limited to the enumerated values, and other values not enumerated in the numerical range are also applicable, and preferably 1 (50-80).
Preferably, the median particle diameter of the flaky porous hard carbon is 1 to 30 μm, and may be, for example, 1 μm, 5 μm, 10 μm, 20 μm or 30 μm, but is not limited to the enumerated values, and other values not enumerated within the numerical range are equally applicable, preferably 15 to 25 μm.
Preferably, the sheet-like, porous, hard carbon has a porosity of 30 to 70%, for example, 30%, 40%, 50%, 60%, or 70%; the specific surface area of the flaky porous hard carbon is 100-500m2G, may be, for example, 100m2/g、200m2/g、300m2/g、400m2G or 500m2The values/g are not limited to the values listed, and other values in the numerical range not listed are equally applicable.
Preferably, the average pore diameter of the plate-like porous hard carbon is 10 to 1000nm, for example, 10nm, 100nm, 500nm, 900nm or 1000nm, but not limited to the enumerated values, and other values not enumerated within the numerical range are equally applicable, preferably 400-800 nm.
Preferably, the nanosilicon-based material has a median particle size of 1 to 100nm, for example 1nm, 20nm, 50nm, 80nm or 100nm, but not limited to the values recited, and other values within the range of values not recited are equally applicable, preferably 70 to 90 nm.
The lithium ion battery negative plate provided by the invention has the advantages that the particle size, the length-diameter ratio and the average pore size of the flaky porous hard carbon and the particle size of the nano silicon-based material are regulated, so that the nano silicon-based material particles can be well dispersed in the pore channel of the hard carbon, and the pore channel can limit the expansion of the nano silicon-based material particles due to the lower expansion performance of the hard carbon, so that the lithium ion battery negative plate with low expansion and high stability is obtained.
Preferably, the conductive agent comprises any one or a combination of at least two of conductive carbon black, graphite powder, or activated carbon, and typical but non-limiting combinations include a combination of conductive carbon black and graphite powder, a combination of conductive carbon black and activated carbon, a combination of activated carbon and graphite powder, or a combination of conductive carbon black, graphite powder, or activated carbon.
Preferably, the binder comprises any one or a combination of at least two of sodium carboxymethylcellulose, styrene-butadiene rubber, polytetrafluoroethylene or polyvinylidene fluoride, typical but non-limiting combinations include sodium carboxymethylcellulose and styrene-butadiene rubber, sodium carboxymethylcellulose and polytetrafluoroethylene, sodium carboxymethylcellulose and polyvinylidene fluoride, styrene-butadiene rubber and polytetrafluoroethylene, styrene-butadiene rubber and polyvinylidene fluoride, polytetrafluoroethylene and polyvinylidene fluoride, sodium carboxymethylcellulose, styrene-butadiene rubber and polytetrafluoroethylene, or sodium carboxymethylcellulose, styrene-butadiene rubber and polytetrafluoroethylene.
Preferably, the lithium supplement material comprises lithium powder and/or lithium foil.
Preferably, the flaky porous hard carbon is obtained by the following method: heating and carbonizing the hard carbon raw material to obtain carbide; adding a stripping agent into the carbide, and stripping to obtain a stripped object; and (4) heating and ventilating, and carrying out pore forming on the obtained stripping substance to obtain the flaky porous hard carbon.
Preferably, the hard carbon feedstock comprises any one or a combination of at least two of phenolic resin, epoxy resin, polystyrene or polyvinyl chloride, typical but non-limiting combinations include combinations of phenolic resin and epoxy resin, phenolic resin and polystyrene, phenolic resin and polyvinyl chloride, epoxy resin and polystyrene, polystyrene and polyvinyl chloride, phenolic resin, epoxy resin and polystyrene, epoxy resin and polyvinyl chloride, phenolic resin, polystyrene and polyvinyl chloride, epoxy resin, polystyrene and polyvinyl chloride, or phenolic resin, epoxy resin, polystyrene and polyvinyl chloride.
Preferably, the median particle size of the hard carbon raw material is 100-200 μm, and may be, for example, 100 μm, 120 μm, 140 μm, 160 μm or 200 μm, but is not limited to the recited values, and other values not recited within the numerical range are also applicable.
The invention controls the median particle size of the flaky porous hard carbon by selecting the median particle size range of the hard carbon raw material. When the median particle diameter of the hard carbon raw material exceeds the particle diameter range provided by the present invention, the median particle diameter of the flaky porous hard carbon exceeds the range provided by the present invention.
Preferably, the temperature for the heat carbonization is 800-.
Preferably, the liquid-solid ratio of the stripping agent to the hard carbon raw material is (1-2):1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1 or 2:1, and the unit of the liquid-solid ratio is mL/g, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the stripping agent comprises a saturated potassium hydroxide solution and/or concentrated sulfuric acid. The mass concentration of the concentrated sulfuric acid is 95-98%.
Preferably, the temperature of the stripping is from 90 to 120 ℃, for example, it may be 90 ℃, 100 ℃, 105 ℃, 110 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the stripping time is 4-6h, for example 4h, 4.5h, 5h, 5.5h or 6h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The stripping time provided by the invention influences the length-diameter ratio of the prepared flaky porous hard carbon, and when the stripping time is less than 4 hours, the stripping effect is poor, and the length-diameter ratio is larger; when the peeling time exceeds 6 hours, the hard carbon structure is easily broken.
Preferably, the temperature of the end point of the temperature rise is 600-800 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the aerated gas comprises any one of oxygen, carbon dioxide or water vapour, typical but non-limiting combinations include oxygen in combination with carbon dioxide, carbon dioxide in combination with water vapour, oxygen in combination with water vapour, or oxygen, carbon dioxide in combination with water vapour.
Preferably, the flow rate of the aeration is 200-400mL/min, such as 200mL/min, 250mL/min, 300mL/min, 350mL/min or 400mL/min, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
The average pore size of the prepared flaky porous hard carbon is influenced by the temperature rise temperature and the ventilation flow rate, and when the temperature rise temperature is higher than 800 ℃, the flaky structure is easily damaged; when the temperature is raised to less than 600 ℃, ineffective closed pores are easily formed. When the ventilation flow rate is more than 400mL/min, the sheet structure is easy to damage, and the average pore diameter is larger; when the aeration flow rate is less than 200mL/min, the average pore diameter is smaller and the porosity is lower.
In a second aspect, the invention provides a preparation method of the lithium ion battery negative electrode sheet according to the first aspect, the preparation method comprises the following steps:
uniformly mixing the binary composite material, the conductive agent, the lithium supplement material and the binder with the formula amount of 40-60 wt% to obtain mixed slurry;
uniformly mixing the obtained mixed slurry, a solvent and the balance of a binder to obtain negative electrode slurry, wherein the solvent comprises water and accounts for 40-60 wt% of the mixed slurry; and
uniformly coating the obtained negative electrode slurry on a negative electrode current collector, and rolling to obtain the lithium ion battery negative electrode plate, wherein the surface density after coating is 5-10mg/cm2The compaction density of the roller compaction is 0.8-1.0g/cm3。
The mass of the solvent is 40 to 60 wt% of the mixed slurry, and may be, for example, 40 wt%, 45 wt%, 50 wt%, 55 wt%, or 60 wt%; the coated surface density is 5-10mg/cm2For example, it may be 5mg/cm2、6mg/cm2、7mg/cm2、8mg/cm2、9mg/cm2Or 10mg/cm2(ii) a The compaction density of the roller compaction is 0.8-1.0g/cm3For example, it may be 0.8g/cm3、0.85g/cm3、0.9g/cm3、0.95g/cm3Or 1.0g/cm3But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
The binder is present in an amount of 40 to 60% by weight, for example 40%, 45%, 50%, 55% or 60% by weight, based on the formulation, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
In a third aspect, the invention provides an application of the lithium ion battery negative electrode sheet according to the first aspect, wherein the lithium ion battery negative electrode sheet is used for a lithium ion battery.
By the technical scheme, the invention has the following beneficial effects:
(1) according to the invention, the prepared lithium ion battery negative plate combines the rapid charging capability and the low expansion performance and has high capacity by compounding the flaky porous hard carbon and the nano silicon-based material. Meanwhile, the first coulomb efficiency of the lithium ion battery negative plate is improved by supplementing lithium to the negative electrode.
(2) The invention makes the nanometer silicon-based material particles disperse in the pore canal of the hard carbon by regulating and controlling the particle size, the length-diameter ratio and the average pore diameter of the flaky porous hard carbon and the particle size of the nanometer silicon-based particles. The pore channel limits the expansion of the nano silicon-based particles, so that the prepared lithium ion battery negative plate has high stability.
Drawings
Fig. 1 is a schematic structural diagram of a negative electrode sheet of a lithium ion battery.
Reference numerals:
1: sheet-shaped porous hard carbon pore canals; 2: nano silicon-based materials; 3: flake porous hard carbon nanosheets.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings by way of specific embodiments. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
In the prior art, one technical scheme provides a method for preparing a silicon-carbon alloy cathode material for a lithium ion battery, which comprises the steps of dispersing nano silicon in an organic solution to form a uniform nano silicon suspension, adding a silane coupling agent into the nano silicon suspension, coating with carbon, and carrying out heat treatment. Compared with the prior art, the silane coupling agent is added, so that the dispersibility of the nano silicon particles in the silicon-carbon composite material is improved, and the volume effect caused by the agglomeration of silicon in the lithium releasing and embedding process is inhibited, so that the cycle performance and the specific capacity of the silicon-carbon composite negative electrode material are improved.
The other technical scheme provides a high-capacity SiOx-based composite negative electrode material, a preparation method and a battery, wherein the negative electrode material comprises a silicon oxide material, a carbon material and an amorphous carbon coating layer, the silicon oxide material is silicon oxide or silicon oxide modified by carbon coating, and the silicon oxide material is coated on the surface of carbon material particles; the mode of combining mechanical fusion and solid phase coating technology is adopted, the uniform dispersion and coating effects of micron-sized silicon oxide particles on the surfaces of carbon material particles are realized, the dispersibility of the silicon oxide particles on the surfaces of the carbon material particles is good, the bonding strength of the silicon oxide particles and the carbon material particles is high, and the cycle performance of the material is greatly improved; and the first efficiency is high.
The technical scheme has the problems of low capacity, low energy density and high expansion performance.
In order to solve the technical problems, the invention provides a lithium ion battery negative plate and a preparation method and application thereof.
In the specific embodiment provided by the invention, the negative electrode plate of the lithium ion battery consists of a sheet-shaped porous hard carbon pore channel 1, a nano silicon-based material 2 in the pore channel and a sheet-shaped porous hard carbon nano plate 3 (see fig. 1). The flake porous hard carbon has large interlayer spacing and controllable pore channels. The pore channel is provided with a through hole structure, so that the rapid de-intercalation of lithium ions is facilitated, the nano silicon-based material can be confined, the nano silicon-based material can be dispersed in the through hole, and the structure of the lithium ion battery negative plate is stable due to the inhibition of the through hole structure when the nano silicon-based material expands. The nanometer silicon-based material is filled in the pore channel, so that the lithium ion battery negative plate has high capacity and good electrochemical performance.
Example 1
The present embodiment provides a lithium ion battery negative electrode plate, which includes:
Figure BDA0003277134210000091
the binary composite material comprises 50% of flaky porous hard carbon by mass and the balance of nano silicon. The median particle diameter of the flaky porous hard carbon is 20 mu m, the length-diameter ratio is 1:70, the average pore diameter is 600nm, the porosity is 50 percent, and the specific surface area is 300m2(ii) in terms of/g. In the nano siliconThe median particle diameter was 80 nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing phenolic resin with the median particle size of 150 mu m at 1000 ℃ to obtain carbide; uniformly mixing 95% concentrated sulfuric acid with the obtained carbide according to the liquid-solid ratio of 1.5:1, and stripping the carbide for 5 hours at 105 ℃ to obtain a stripped substance; and (3) heating to 700 ℃, and carrying out pore-forming on the obtained stripping substance under the oxygen atmosphere with the flow rate of 300mL/min to obtain the flaky porous hard carbon.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, the nano silicon, the conductive carbon black, the lithium powder and the sodium carboxymethyl cellulose according to the formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene butadiene rubber and water with the mass of 50 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 7mg/cm2The compacted density after rolling is 0.9g/cm3And obtaining the lithium ion battery negative plate.
Example 2
The present embodiment provides a lithium ion battery negative electrode plate, which includes:
Figure BDA0003277134210000101
the binary composite material comprises 40% of flaky porous hard carbon by mass and the balance of nano silicon. The median particle diameter of the flaky porous hard carbon is 15 mu m, the length-diameter ratio is 1:50, the average pore diameter is 400nm, the porosity is 40 percent, and the specific surface area is 200m2(ii) in terms of/g. The median particle size of the nano silicon is 90 nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing at 900 ℃ the epoxy resin with the median particle size of 125 mu m to obtain carbide; uniformly mixing a saturated potassium hydroxide solution and the obtained carbide according to a liquid-solid ratio of 1.2:1, and stripping the carbide for 4.5 hours at the temperature of 100 ℃ to obtain a stripped substance; and (3) heating to 750 ℃, and carrying out pore-forming on the obtained stripping substance under the steam atmosphere with the flow rate of 250mL/min to obtain the flaky porous hard carbon.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, nano silicon, conductive carbon black, graphite powder, lithium foil and 40% of polytetrafluoroethylene according to the formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, the residual polytetrafluoroethylene and water with the mass of 55 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 6mg/cm2The compacted density after rolling is 0.85g/cm3And obtaining the lithium ion battery negative plate.
Example 3
The present embodiment provides a lithium ion battery negative electrode plate, which includes:
Figure BDA0003277134210000111
the binary composite material comprises 80% of flaky porous hard carbon by mass and the balance of nano silicon. The median particle diameter of the flaky porous hard carbon is 25 mu m, the length-diameter ratio is 1:80, the average pore diameter is 800nm, the porosity is 60 percent, and the specific surface area is 400m2(ii) in terms of/g. The median particle size of the nano silicon carbon is 70 nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing polystyrene with the median particle size of 175 mu m at 1200 ℃ to obtain carbide; uniformly mixing a saturated potassium hydroxide solution with the obtained carbide according to a liquid-solid ratio of 1.7:1, and stripping the obtained carbide for 5.5 hours at the temperature of 110 ℃ to obtain a stripped substance; and (3) heating to 650 ℃, and carrying out pore-forming on the obtained stripping substance under the carbon dioxide atmosphere with the flow rate of 350mL/min to obtain the flaky porous hard carbon.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, nano silicon, graphite powder, sodium carboxymethylcellulose, lithium foil and 50 wt% of polytetrafluoroethylene according to the formula ratio to obtain mixed slurry; uniformityMixing the obtained mixed slurry, styrene butadiene rubber and water with the mass of 45 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 8mg/cm2The compacted density after rolling is 0.95g/cm3And obtaining the lithium ion battery negative plate.
Example 4
The present embodiment provides a lithium ion battery negative electrode plate, which includes:
Figure BDA0003277134210000112
Figure BDA0003277134210000121
the binary composite material comprises 90% of flaky porous hard carbon by mass and the balance of nano silicon. The median particle diameter of the flaky porous hard carbon is 1 mu m, the length-diameter ratio is 1:5, the average pore diameter is 10nm, the porosity is 30 percent, and the specific surface area is 100m2(ii) in terms of/g. The median particle size of the nano silicon is 100 nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating polyvinyl chloride with a median particle size of 100 mu m at 800 ℃ for carbonization to obtain carbide; uniformly mixing 98% concentrated sulfuric acid with the obtained carbide according to the liquid-solid ratio of 1:1, and stripping the obtained carbide for 4 hours at 90 ℃ to obtain a stripped substance; and (3) heating to 800 ℃, and carrying out pore-forming on the obtained stripping substance under the oxygen atmosphere with the flow rate of 200mL/min to obtain the flaky porous hard carbon.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, nano silicon, conductive carbon black, graphite powder, activated carbon, 60 wt% of sodium carboxymethylcellulose and lithium powder according to the formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, 40 wt% of sodium carboxymethyl cellulose and 40 wt% of water by mass of the mixed slurry to obtain negative electrode slurry; the obtained negative pole slurry is evenly coated on a negative pole current collector, and the surface density is 5 mg-cm2The compacted density after rolling is 0.8g/cm3And obtaining the lithium ion battery negative plate.
Example 5
The present embodiment provides a lithium ion battery negative electrode plate, which includes:
Figure BDA0003277134210000122
Figure BDA0003277134210000131
the binary composite material comprises 10% of flaky porous hard carbon by mass and the balance of nano silicon. The median particle diameter of the flaky porous hard carbon is 30 mu m, the length-diameter ratio is 1:100, the average pore diameter is 1000nm, the porosity is 70 percent, and the specific surface area is 500m2(ii) in terms of/g. The median particle size of the nano silicon is 1 nm.
The preparation method of the flaky porous hard carbon comprises the following steps: carrying out heating carbonization at 800 ℃ on polyvinyl chloride with the median particle size of 100 mu m to obtain carbide; uniformly mixing 97% concentrated sulfuric acid with the obtained carbide according to the liquid-solid ratio of 2:1, and stripping the obtained carbide for 4 hours at 90 ℃ to obtain a stripped substance; and (3) heating to 800 ℃, and carrying out pore-forming on the obtained stripping substance under the oxygen atmosphere with the flow rate of 200mL/min to obtain the flaky porous hard carbon.
Heating and carbonizing polystyrene with a median particle size of 200 μm at 1500 deg.C to obtain carbide; uniformly mixing concentrated sulfuric acid with the obtained carbide according to the liquid-solid ratio of 1:2, and stripping the obtained carbide for 6 hours at 120 ℃ to obtain a stripped substance; and (3) heating to 600 ℃, and carrying out pore-forming on the obtained stripping substance under the oxygen atmosphere with the flow rate of 400mL/min to obtain the flaky porous hard carbon.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, nano silicon, activated carbon, sodium carboxymethyl cellulose, polytetrafluoroethylene and lithium powder according to the formula ratio to obtain mixed slurry; mix evenlyMixing the obtained mixed slurry, styrene butadiene rubber, polyvinylidene fluoride and water with the mass of 60 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 10mg/cm2The compacted density after rolling is 1g/cm3And obtaining the lithium ion battery negative plate.
Example 6
This example provides a negative electrode plate for a lithium ion battery, which is prepared under the same conditions as in example 1 except that the median particle size of the phenolic resin is 80 μm when the flaky porous hard carbon is prepared.
Since the particle diameter of the phenolic resin was changed to 80 μm, the median particle diameter of the produced flaky porous hard carbon was 0.5 μm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 7
This example provides a negative electrode plate for a lithium ion battery, which is prepared under the same conditions as in example 1 except that the median particle size of the phenolic resin is 300 μm when the flaky porous hard carbon is prepared.
Since the particle diameter of the phenolic resin was changed to 300 μm, the median particle diameter of the produced flaky porous hard carbon was 35 μm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 8
This example provides a negative electrode plate of a lithium ion battery, and the conditions for preparing the flaky porous hard carbon are the same as those in example 1 except that the peeling time for preparing the flaky porous hard carbon is 2 hours.
Since the peeling time was changed to 2 hours, the aspect ratio of the produced flaky porous hard carbon was 1: 2.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 9
This example provides a negative electrode sheet for a lithium ion battery, and the conditions for preparing a sheet-like porous hard carbon are the same as in example 1 except that the peeling time for preparing the sheet-like porous hard carbon is 8 hours.
Since the peeling time was changed to 8 hours, the aspect ratio of the produced flaky porous hard carbon was 1: 110.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 10
This example provides a negative electrode plate of a lithium ion battery, which is prepared under the same conditions as in example 1 except that the temperature of the negative electrode plate is 500 ℃ and the flow rate of oxygen is 100 mL/min.
The temperature is increased to 500 ℃, the flow rate of oxygen is changed to 100mL/min, and the average pore diameter of the prepared flaky porous hard carbon is less than 10 nm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 11
This example provides a negative electrode plate of a lithium ion battery, which is prepared under the same conditions as in example 1 except that the temperature of the negative electrode plate is 1000 ℃ and the flow rate of oxygen is 500 mL/min.
The temperature is increased to 1000 ℃, the flow rate of oxygen is changed to 500mL/min, and the average pore diameter of the prepared flaky porous hard carbon is larger than 1000 nm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 12
The present embodiment provides a lithium ion battery negative electrode plate, which has the same composition content as in example 1, except that the median particle size of the nano-silicon is 0.8 nm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Example 13
The present example provides a lithium ion battery negative electrode plate, which has the same composition content as in example 1, except that the median particle size of the nano-silicon is 105 nm.
The composition and the preparation method of the negative electrode plate of the rest lithium ion batteries in the embodiment are the same as those in the embodiment 1.
Comparative example 1
This comparative example provides a lithium ion battery negative pole piece, lithium ion battery negative pole piece includes:
Figure BDA0003277134210000151
Figure BDA0003277134210000161
the median particle diameter of the flaky porous hard carbon is 20 mu m, the length-diameter ratio is 1:70, the average pore diameter is 600nm, the porosity is 50 percent, and the specific surface area is 300m2(ii) in terms of/g. The preparation method of the flaky porous hard carbon is the same as that of example 1.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, the conductive carbon black, the lithium powder and the sodium carboxymethyl cellulose according to the formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene butadiene rubber and water with the mass of 50 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 7mg/cm2The compacted density after rolling is 0.9g/cm3And obtaining the lithium ion battery negative plate.
Comparative example 2
This comparative example provides a lithium ion battery negative pole piece, lithium ion battery negative pole piece includes:
Figure BDA0003277134210000162
the median particle size of the nano silicon is 80 nm.
The preparation method of the lithium ion battery negative plate comprisesThe method comprises the following steps: uniformly mixing nano silicon, conductive carbon black, lithium powder and sodium carboxymethyl cellulose in a formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene butadiene rubber and water with the mass of 50 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 7mg/cm2The compacted density after rolling is 0.9g/cm3And obtaining the lithium ion battery negative plate.
Comparative example 3
The comparative example provides a lithium ion battery negative plate, and the content of the components of the lithium ion battery negative plate is the same as that of the lithium ion battery negative plate in example 1 except that 0.8 part of lithium powder is not added.
The preparation method of the flake shaped porous hard carbon of this comparative example was the same as that of example 1.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing the flaky porous hard carbon, the nano silicon, the conductive carbon black and the sodium carboxymethyl cellulose according to the formula ratio to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene butadiene rubber and water with the mass of 50 wt% of the mixed slurry to obtain negative electrode slurry; the obtained negative electrode slurry is uniformly coated on a negative electrode current collector, and the surface density is 7mg/cm2The compacted density after rolling is 0.9g/cm3And obtaining the lithium ion battery negative plate.
Comparative example 4
This comparative example provides a lithium ion battery negative pole piece, lithium ion battery negative pole piece includes:
Figure BDA0003277134210000171
the binary composite material comprises 50% of common hard carbon by mass and the balance of nano silicon; the median particle size of the conventional hard carbon is 20 μm, and the median particle size of the nano silicon is 80 nm.
The present comparative example provides that the method for preparing the general hard carbon includes the steps of: and heating and carbonizing the phenolic resin with the median particle size of 150 mu m at 1000 ℃ to obtain the common hard carbon.
The preparation method of the lithium ion battery negative plate of the comparative example has the same process steps and parameters as those of the example 1 except that the sheet-shaped porous hard carbon is replaced by the conventional hard carbon.
Assembling the lithium ion battery negative electrode sheets and the lithium ion battery lithium sheets of the examples 1 to 13 and the comparative examples 1 to 4 into a CR2016 button type half cell for gram capacity determination; assembling the lithium ion battery negative electrode sheets of the examples 1 to 13 and the lithium ion battery negative electrode sheets of the comparative examples 1 to 4 and the ternary material into a lithium ion full battery for performance measurement, charging the full battery to the upper limit cut-off voltage at a constant current of 0.33C, then charging the full battery to 0.05C at a constant voltage, then discharging the full battery to the lower limit cut-off voltage at a constant current of 0.33C, and calculating the first coulombic efficiency of the full battery; and charging the full battery to the upper limit cut-off voltage at constant current of 0.33C, then charging the full battery to 0.05C at constant voltage, and disassembling the full-charge full battery to measure the expansion rate of the negative pole piece. The full battery is charged to the upper limit cut-off voltage at a constant current of 0.5C, then charged to 0.05C at a constant voltage, and then discharged to the lower limit cut-off voltage at a constant current of 0.5C, and the discharge capacity ratio of the 100 th circle and the 1 st circle is recorded as the cycle capacity retention ratio after 100 times of charging and discharging, and the result is shown in Table 1.
TABLE 1
Figure BDA0003277134210000181
Figure BDA0003277134210000191
From the data in table 1, the following conclusions can be drawn:
(1) from embodiments 1 to 5, it can be seen that the lithium ion battery negative electrode sheet provided by the invention has high capacity, low expansion, high cycle capacity retention rate, overcomes the defects of a single hard carbon and a single silicon material, and has high first coulombic efficiency by compounding the flaky porous hard carbon with the nano silicon-based material and regulating and controlling the particle size, the length-diameter ratio, the pore diameter and the particle size of the flaky porous hard carbon and the particle size of the nano silicon-based particles.
(2) It can be known from the comparison between examples 6 and 7 and example 1 that when the median particle diameter of the flaky porous hard carbon is not within the preferred range provided by the present invention, the nano-silicon cannot be well filled in the pore channels of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor retention rate of cycle capacity, which indicates that the median particle diameter range of the flaky porous hard carbon provided by the present invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is helpful for preparing a lithium ion battery with high capacity, low expansion and long cycle life.
(3) It can be known from the comparison between examples 8 and 9 and example 1 that when the aspect ratio of the flaky porous hard carbon is not within the preferred range provided by the present invention, the nano-silicon cannot be well filled in the pore channels of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor retention rate of the cycle capacity, which indicates that the aspect ratio range of the flaky porous hard carbon provided by the present invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is helpful for preparing the lithium ion battery with high capacity, low expansion and long cycle life.
(4) It can be known from the comparison between examples 10 and 11 and example 1 that when the average pore diameter of the flaky porous hard carbon is not within the preferred range provided by the present invention, the nano-silicon cannot be well filled in the pore channels of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate and poor cycle capacity retention rate, which indicates that the pore diameter range of the flaky porous hard carbon provided by the present invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is helpful for preparing a lithium ion battery with high capacity, low expansion and high energy density.
(5) It can be known from the comparison between examples 12 and 13 and example 1 that, when the median particle diameter of the nano-silicon is not within the preferable range provided by the present invention, the nano-silicon cannot be well filled in the pore channels of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor retention rate of the cycle capacity, which indicates that the median particle diameter range of the nano-silicon provided by the present invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is helpful for preparing the lithium ion battery with high capacity, low expansion and high energy density.
(6) It can be known from comparison of comparative examples 1 and 2 with example 1 that, when the lithium ion battery negative electrode sheet does not compound hard carbon and nano silicon, the lithium ion battery prepared by using the sheet-shaped porous hard carbon as the main raw material has low capacity, and the lithium ion battery prepared by using the nano silicon has high expansion rate and poor cycle capacity retention rate, which indicates that the lithium ion battery negative electrode sheet provided by the invention overcomes the defects of the hard carbon and the nano silicon by compounding the sheet-shaped porous hard carbon and the nano silicon, and the lithium ion battery with excellent performance of the composite material is prepared.
(7) Compared with the comparative example 3 and the example 1, it can be known that the lithium ion battery prepared by the method has low first coulombic efficiency when the lithium ion battery negative plate is not added with the lithium supplement material, which shows that the lithium supplement material provided by the invention is an important material for preparing the lithium ion battery negative plate made of the composite material of hard carbon and nano silicon. The first coulombic efficiency of the composite material lithium ion battery is improved by supplementing lithium to the negative electrode.
(8) It can be seen from the comparison between comparative example 4 and example 1 that when the non-sheet non-porous conventional hard carbon material is used, the prepared lithium ion battery has high expansion rate and poor cycle capacity retention rate, which indicates that the hard carbon material with the sheet porous property provided by the invention is an important property of the lithium ion battery cathode sheet, and is beneficial to preparing the lithium ion battery with high capacity, low expansion and high energy density.
In conclusion, the lithium ion battery negative plate prepared by compounding the flaky porous hard carbon and the nano silicon-based material has both low expansion performance and long cycle performance and has high capacity. Meanwhile, the first coulomb efficiency of the lithium ion battery negative plate is improved by supplementing lithium to the negative electrode. The particle size, the length-diameter ratio and the pore diameter of the flaky porous hard carbon and the particle size of the nano silicon-based particles are regulated and controlled, so that the nano silicon particles are dispersed in the pore channels of the hard carbon. The pore channel limits the expansion of the nano silicon particles, so that the prepared lithium ion battery negative plate has high stability.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The lithium ion battery negative plate is characterized by comprising the following components in parts by weight:
Figure FDA0003277134200000011
the binary composite material is a composite material of flaky porous hard carbon and a nano silicon-based material.
2. The lithium ion battery negative electrode sheet according to claim 1, wherein the binary composite material comprises 10 to 90 wt% of the sheet-shaped porous hard carbon, and the balance is the nano silicon-based material;
preferably, the mass percentage of the flaky porous hard carbon in the binary composite material is 40-80 wt%.
3. The lithium ion battery negative electrode sheet according to claim 1 or 2, wherein the aspect ratio of the sheet-shaped porous hard carbon is 1 (5-100), preferably 1 (50-80);
preferably, the median particle diameter of the flaky porous hard carbon is 1 to 30 μm, preferably 15 to 25 μm.
4. The lithium ion battery negative electrode sheet according to any one of claims 1 to 3, wherein the sheet-shaped porous hard carbon has a porosity of 30% to 70%, and a specific surface area of 100-500m2/g；
Preferably, the average pore diameter of the flaky porous hard carbon is 10-1000nm, preferably 400-800 nm.
5. The negative electrode plate of the lithium ion battery according to any one of claims 1 to 4, wherein the median particle diameter of the nano silicon-based material is 1 to 100nm, preferably 70 to 90 nm.
6. The lithium ion battery negative electrode sheet according to any one of claims 1 to 5, wherein the conductive agent comprises any one of conductive carbon black, graphite powder or activated carbon or a combination of at least two of the conductive carbon black, graphite powder or activated carbon;
preferably, the binder comprises any one or a combination of at least two of sodium carboxymethylcellulose, styrene-butadiene rubber, polytetrafluoroethylene or polyvinylidene fluoride;
preferably, the lithium supplement material comprises lithium powder and/or lithium foil.
7. The negative electrode sheet for the lithium ion battery according to any one of claims 1 to 6, wherein the sheet-like porous hard carbon is obtained by a method comprising: heating and carbonizing the hard carbon raw material to obtain carbide; uniformly mixing the obtained carbide and a stripping agent, and stripping to obtain a stripped substance; and (4) heating and ventilating, and carrying out pore forming on the obtained stripping substance to obtain the flaky porous hard carbon.
8. The lithium ion battery negative electrode sheet according to claim 7, wherein the hard carbon raw material comprises any one of or a combination of at least two of phenolic resin, epoxy resin, polystyrene or polyvinyl chloride;
preferably, the median particle size of the hard carbon feedstock is 100-;
preferably, the temperature for heating and carbonizing is 800-1500 ℃;
preferably, the stripping agent comprises a saturated potassium hydroxide solution and/or concentrated sulfuric acid;
preferably, the liquid-solid ratio of the stripping agent to the hard carbon raw material is (1-2):1, and the unit of the liquid-solid ratio is mL/g;
preferably, the temperature of stripping is 90-120 ℃;
preferably, the stripping time is 4-6 h;
preferably, the temperature rise end temperature is 600-800 ℃;
preferably, the aerated gas comprises any one or a combination of at least two of oxygen, carbon dioxide or water vapour;
preferably, the flow rate of the aeration is 200-400 mL/min.
9. The preparation method of the negative electrode plate of the lithium ion battery according to any one of claims 1 to 8, wherein the preparation method comprises the following steps:
uniformly mixing the binary composite material, the conductive agent, the lithium supplement material and the binder with the formula amount of 40-60 wt% to obtain mixed slurry;
uniformly mixing the obtained mixed slurry, a solvent and the balance of a binder to obtain negative electrode slurry, wherein the solvent comprises water and accounts for 40-60 wt% of the mixed slurry; and
uniformly coating the obtained negative electrode slurry on a negative electrode current collector, and rolling to obtain the lithium ion battery negative electrode plate, wherein the surface density after coating is 5-10mg/cm2The compaction density of the roller compaction is 0.8-1.0g/cm3。
10. Use of the negative electrode sheet according to any one of claims 1 to 8, wherein the negative electrode sheet is used in a lithium ion battery.
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