CN113871574B - 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

Info

Publication number
CN113871574B
CN113871574B CN202111120966.5A CN202111120966A CN113871574B CN 113871574 B CN113871574 B CN 113871574B CN 202111120966 A CN202111120966 A CN 202111120966A CN 113871574 B CN113871574 B CN 113871574B
Authority
CN
China
Prior art keywords
ion battery
lithium ion
hard carbon
negative electrode
battery negative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111120966.5A
Other languages
Chinese (zh)
Other versions
CN113871574A (en
Inventor
刘永兴
李若楠
王水良
王彦青
请求不公布姓名
孙化雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Original Assignee
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Envision Power Technology Jiangsu Co Ltd, Envision Ruitai Power Technology Shanghai Co Ltd filed Critical Envision Power Technology Jiangsu Co Ltd
Priority to CN202111120966.5A priority Critical patent/CN113871574B/en
Publication of CN113871574A publication Critical patent/CN113871574A/en
Application granted granted Critical
Publication of CN113871574B publication Critical patent/CN113871574B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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, 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 supplementing material; wherein the binary composite material is a composite material of flaky porous hard carbon and nano silicon-based material. According to the invention, the flaky porous hard carbon is compounded with the nano silicon-based material, and the prepared lithium ion battery negative electrode tablet has the quick charge capability and 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 through negative electrode lithium supplement, 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, in particular to a negative electrode material, 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 multiplying power performance, and the ultra-long endurance and super fast charging are key development directions of the next generation lithium ion battery. Pure graphite materials cannot meet the requirements, and negative electrode materials with higher energy density and better rapid charging performance are required to be developed. In addition to graphite materials, the hard carbon material is a novel negative electrode material, has the advantages of high capacity, good power and low expansion compared with the graphite materials, but has low coulombic efficiency for the first time; silicon-based materials are also considered to be relatively promising negative electrode materials, which have higher capacities, but lower initial coulombic efficiencies and poorer rate capability.
In the prior art, a graphite/silicon-based material composite mode is generally adopted to achieve both energy density and quick charge performance, but the quick charge performance of graphite basically reaches the limit, and the space for continuous promotion is not large. Simultaneously, the expansion of the silicon-based material and the graphite material is bigger, so that the structural stability of the battery cell is easily damaged in the cyclic charge and discharge process, and the cyclic attenuation is faster.
Therefore, how to break through the limitation of the traditional graphite material and prepare the lithium ion battery negative plate with the novel negative electrode material, so that the lithium ion battery negative plate has the fast charging capability and the low expansion capability of the hard carbon material and the high capacity performance of the silicon-based material, and meanwhile, has high first coulombic efficiency, and is a problem to be solved 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 electrode sheet, a preparation method and application thereof, wherein the lithium ion battery negative electrode sheet has the fast charging capability and low expansion capability of a hard carbon material and the high capacity performance of a silicon-based material, and simultaneously has high first coulombic efficiency and good stability.
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 includes, in parts by weight:
the binary composite material is a composite material of flaky porous hard carbon and nano silicon-based materials.
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 cathode material with higher capacity, but has high expansion rate, poor rate capability and low first coulombic efficiency. The lithium ion battery negative plate is prepared by compounding the hard carbon and the silicon material, so that the advantages of the two materials are considered, and the defects of the two materials are improved. Meanwhile, the low first coulombic efficiency of the hard carbon and the silicon material can be improved by adding the lithium supplementing material.
The weight part of the binary composite material in the lithium ion battery negative plate is 98-102 parts, for example, 98 parts, 99 parts, 100 parts, 101 parts or 102 parts, but the binary composite material is not limited to the listed values, and other non-listed values in the numerical range are 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 parts, 0.7 parts, 1 parts, 1.2 parts or 1.5 parts, but is not limited to the listed values, and other non-listed values in the numerical range are 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 is not limited to the listed values, and other non-listed values in the range of values are equally applicable.
The weight part of the lithium supplementing 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 parts or 2 parts, but the lithium supplementing material is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the mass percentage of the flaky porous hard carbon in the binary composite material is 10-90wt%, such as 10wt%, 30wt%, 50wt%, 70wt% or 90wt%, but is not limited to the recited values, other non-recited values in the numerical range are equally 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 40-80wt%, such as 40wt%, 50wt%, 60wt%, 70wt% or 80wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the aspect ratio of the flaky porous hard carbon is 1 (5-100), for example, 1:5, 1:20, 1:40, 1:80 or 1:100, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 1 (50-80).
Preferably, the median particle diameter of the flaky porous hard carbon is 1 to 30. Mu.m, for example, 1 μm, 5 μm, 10 μm, 20 μm or 30 μm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 15 to 25. Mu.m.
Preferably, the porosity of the flaky porous hard carbon is 30-70%, for example, 30%, 40%, 50%, 60% or 70%; the specific surface area of the flaky porous hard carbon is 100-500m 2 /g, for example, may be 100m 2 /g、200m 2 /g、300m 2 /g、400m 2 /g or 500m 2 The values of/g are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the average pore diameter of the flaky porous hard carbon is 10 to 1000nm, for example, 10nm, 100nm, 500nm, 900nm or 1000nm, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable, preferably 400 to 800nm.
Preferably, the median particle diameter of the nano silicon-based material is 1-100nm, for example, 1nm, 20nm, 50nm, 80nm or 100nm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 70-90nm.
According to the lithium ion battery negative electrode plate, 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 canal of the hard carbon, and the pore canal can limit the expansion of the nano silicon-based material particles due to the low expansion performance of the hard carbon, so that the lithium ion battery negative electrode 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, typically but not limited to 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 carboxymethyl cellulose, styrene-butadiene rubber, polytetrafluoroethylene or polyvinylidene fluoride, and typical but non-limiting combinations include sodium carboxymethyl cellulose in combination with styrene-butadiene rubber, sodium carboxymethyl cellulose in combination with polytetrafluoroethylene, sodium carboxymethyl cellulose in combination with polyvinylidene fluoride, styrene-butadiene rubber in combination with polytetrafluoroethylene, styrene-butadiene rubber in combination with polyvinylidene fluoride, polytetrafluoroethylene in combination with polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber in combination with polytetrafluoroethylene, or sodium carboxymethyl cellulose, styrene-butadiene rubber, polytetrafluoroethylene in combination with polyvinylidene fluoride.
Preferably, the lithium supplementing material comprises lithium powder and/or lithium foil.
Preferably, the sheet-like porous hard carbon is obtained by the following method: heating and carbonizing a hard carbon raw material to obtain carbide; adding a stripping agent into the carbide to strip to obtain a stripped product; heating and ventilating, and pore-forming the obtained stripped material 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, typically but not limited to a combination of phenolic resin and epoxy resin, a combination of phenolic resin and polystyrene, a combination of phenolic resin and polyvinyl chloride, a combination of epoxy resin and polystyrene, a combination of polystyrene and polyvinyl chloride, a combination of phenolic resin, epoxy resin and polystyrene, a combination of phenolic resin, epoxy resin and polyvinyl chloride, a combination of phenolic resin, polystyrene and polyvinyl chloride, a combination of epoxy resin, polystyrene and polyvinyl chloride, or a combination of phenolic resin, epoxy resin, polystyrene and polyvinyl chloride.
Preferably, the hard carbon feedstock has a median particle size of 100-200 μm, which may be, for example, 100 μm, 120 μm, 140 μm, 160 μm or 200 μm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
The invention adjusts and controls the median particle diameter of the flaky porous hard carbon by selecting the median particle diameter range of the hard carbon raw material. When the median particle diameter of the hard carbon raw material exceeds the range of the particle diameter 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 of the heating carbonization is 800-1500 ℃, for example, 800 ℃, 1000 ℃, 1200 ℃, 1400 ℃ or 1500 ℃, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
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 the stripping agent is not limited to the listed values, and other non-listed values in the numerical range are equally 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 stripping temperature is 90-120 ℃, for example, 90 ℃,100 ℃,105 ℃,110 ℃ or 120 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the peeling time is 4-6h, for example, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other non-recited values within 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 end temperature of the temperature rise is 600-800 ℃, for example 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the vented gas comprises any one of oxygen, carbon dioxide or water vapor, typical but non-limiting combinations include combinations of oxygen and carbon dioxide, combinations of carbon dioxide and water vapor, combinations of oxygen and water vapor, or combinations of oxygen, carbon dioxide and water vapor.
Preferably, the ventilation flow rate is 200-400mL/min, for example, 200mL/min, 250mL/min, 300mL/min, 350mL/min or 400mL/min, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The temperature rise temperature and the ventilation flow rate provided by the invention influence the average pore size of the prepared flaky porous hard carbon, and when the temperature rise temperature is higher than 800 ℃, the flaky structure is easily damaged; when the temperature is less than 600 ℃, ineffective closed cells are easily formed. When the ventilation flow rate is more than 400mL/min, the flaky structure is easy to break, 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 present invention provides a method for preparing a negative electrode sheet of a lithium ion battery according to the first aspect, the method comprising the steps of:
uniformly mixing binary composite material, conductive agent and lithium supplementing material with 40-60wt% adhesive to obtain mixed slurry;
uniformly mixing the obtained mixed slurry, a solvent and the balance of binder to obtain negative electrode slurry, wherein the solvent comprises water, and the mass of the solvent is 40-60wt% 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/cm 2 The compacted density of the rolling is 0.8-1.0g/cm 3 。
The mass of the solvent is 40-60wt% of the mixed slurry, for example, 40wt%, 45wt%, 50wt%, 55wt% or 60wt%; the surface density after coating is 5-10mg/cm 2 For example, it may be 5mg/cm 2 、6mg/cm 2 、7mg/cm 2 、8mg/cm 2 、9mg/cm 2 Or 10mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The compaction density of the rolling is 0.8-1.0g/cm 3 For example, it may be 0.8g/cm 3 、0.85g/cm 3 、0.9g/cm 3 、0.95g/cm 3 Or 1.0g/cm 3 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
The binder may be present in an amount of 40-60wt% of the formulation, for example 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
In a third aspect, the present 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) The lithium ion battery negative plate prepared by compounding the flaky porous hard carbon with the nano silicon-based material has both rapid charging capability and low expansion performance and has high capacity. Meanwhile, the first coulomb efficiency of the negative plate of the lithium ion battery is improved through lithium supplementation of the negative electrode.
(2) According to the invention, the particle size, the length-diameter ratio, the average pore diameter and the particle size of the nano silicon-based particles of the flaky porous hard carbon are regulated, so that the nano silicon-based material particles are dispersed in the pore canal of the hard carbon. The pore canal 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 lithium ion battery negative electrode sheet.
Reference numerals:
1: the sheet is provided with Kong Yingtan pore canals; 2: a nano silicon-based material; 3: flake-shaped porous hard carbon nanoplatelets.
Detailed Description
The invention will be described in further detail by means of specific embodiments with reference to the accompanying drawings. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
In the prior art, a technical scheme provides a method for preparing a silicon-carbon alloy anode material for a lithium ion battery, wherein nano silicon is dispersed in an organic solution to form uniform nano silicon suspension, and a silane coupling agent is added into the nano silicon suspension, coated with carbon and subjected to heat treatment. Compared with the prior art, the silane coupling agent is added, so that the dispersibility of nano silicon particles in the silicon-carbon composite material is improved, and the volume effect caused by agglomeration of silicon in the lithium intercalation process is inhibited, so that the cycle performance and specific capacity of the silicon-carbon composite negative electrode material are improved.
The other technical scheme provides a high-capacity SiOx-based composite anode material, a preparation method and a battery, wherein the anode 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 surfaces of carbon material particles; the method has the advantages that the mode of combining mechanical fusion and solid phase coating technology is adopted, the effects of uniform dispersion and coating of the micron-sized silicon oxide particles on the surfaces of the carbon material particles are realized, the silicon oxide particles have good dispersibility on the surfaces of the carbon material particles, 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 time of efficiency is high.
The technical proposal 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, a preparation method and application thereof, wherein the lithium ion battery negative plate has high capacity, high energy density and low expansion performance.
In the specific embodiment provided by the invention, the lithium ion battery negative electrode plate consists of a flaky porous hard carbon pore canal 1, a nano silicon-based material 2 in the pore canal and a flaky porous hard carbon nano plate 3 (see figure 1). The flaky porous hard carbon has large interlayer spacing and adjustable pore channels. The pore canal has a structure of a through hole, is favorable for rapid deintercalation of lithium ions, can limit the domain of the nano silicon-based material, can disperse the nano silicon-based material in the through hole, is restrained by the structure of the through hole when expanding, and ensures that the structure of the negative plate of the lithium ion battery is stable. The nanometer silicon-based material is filled in the pore canal, so that the lithium ion battery negative plate has high capacity and good electrochemical performance.
Example 1
The embodiment provides a lithium ion battery negative plate, the lithium ion battery negative plate includes:
the mass percentage of the flaky porous hard carbon in the binary composite material is 50 percent, and the balance is nano silicon. The flaky porous hard carbon has a median particle diameter of 20 mu m, an aspect ratio of 1:70, an average pore diameter of 600nm, a porosity of 50% and a specific surface area of 300m 2 And/g. The median particle diameter of the nano silicon is 80nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing phenolic resin with a median particle size of 150 μm at 1000 ℃ to obtain carbide; uniformly mixing 95% concentrated sulfuric acid and the obtained carbide according to a liquid-solid ratio of 1.5:1, and stripping the carbide for 5 hours at 105 ℃ to obtain a stripped product; heating to 700 ℃, and pore-forming the obtained stripping material 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: are allUniformly mixing the flaky porous hard carbon, nano silicon, conductive carbon black, lithium powder and sodium carboxymethyl cellulose according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber and water with the mass of 50wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 7mg/cm 2 The compacted density after rolling is 0.9g/cm 3 And obtaining the lithium ion battery negative plate.
Example 2
The embodiment provides a lithium ion battery negative plate, the lithium ion battery negative plate includes:
the mass percentage of the flaky porous hard carbon in the binary composite material is 40 percent, and the balance is nano silicon. The flaky porous hard carbon has a median particle diameter of 15 mu m, an aspect ratio of 1:50, an average pore diameter of 400nm, a porosity of 40% and a specific surface area of 200m 2 And/g. The median particle diameter of the nano silicon is 90nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing the epoxy resin with the median particle size of 125 mu m at 900 ℃ to obtain carbide; uniformly mixing saturated potassium hydroxide solution and the obtained carbide according to the liquid-solid ratio of 1.2:1, and stripping the carbide for 4.5 hours at the temperature of 100 ℃ to obtain a stripped product; heating to 750 ℃, and pore-forming the obtained stripping material 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% polytetrafluoroethylene according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, the rest polytetrafluoroethylene and 55wt% of water of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 6mg/cm 2 The compacted density after rolling is 0.85g/cm 3 And obtaining the lithium ion battery negative plate.
Example 3
The embodiment provides a lithium ion battery negative plate, the lithium ion battery negative plate includes:
the mass percentage of the flaky porous hard carbon in the binary composite material is 80 percent, and the balance is nano silicon. The flaky porous hard carbon has a median particle diameter of 25 mu m, an aspect ratio of 1:80, an average pore diameter of 800nm, a porosity of 60% and a specific surface area of 400m 2 And/g. The median particle diameter of the nano silicon carbon is 70nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing polystyrene with a median particle size of 175 mu m at 1200 ℃ to obtain carbide; uniformly mixing saturated potassium hydroxide solution and the obtained carbide according to a liquid-solid ratio of 1.7:1, and stripping the obtained carbide for 5.5 hours at 110 ℃ to obtain a stripped material; heating to 650 ℃, and pore-forming the obtained stripping material 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 flaky porous hard carbon, nano silicon, graphite powder, sodium carboxymethylcellulose, lithium foil and 50wt% of polytetrafluoroethylene according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber and water with the mass of 45wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 8mg/cm 2 The compacted density after rolling is 0.95g/cm 3 And obtaining the lithium ion battery negative plate.
Example 4
The embodiment provides a lithium ion battery negative plate, the lithium ion battery negative plate includes:
the mass percentage of the flaky porous hard carbon in the binary composite material is 90%, and the balance is nano silicon. The flaky porous hard carbon has a median particle diameter of 1 mu m, an aspect ratio of 1:5, an average pore diameter of 10nm, a porosity of 30% and a specific surface area of 100m 2 And/g. The median particle diameter of the nano silicon is 100nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing polyvinyl chloride with a median particle size of 100 μm at 800 ℃ to obtain carbide; uniformly mixing 98% concentrated sulfuric acid and the obtained carbide according to a liquid-solid ratio of 1:1, and stripping the obtained carbide for 4 hours at 90 ℃ to obtain a stripped material; heating to 800 ℃, and pore-forming the obtained stripping material 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, active carbon, 60wt% of sodium carboxymethylcellulose and lithium powder according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, 40wt% of sodium carboxymethylcellulose and 40wt% of water by mass of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 5mg/cm 2 Compaction density after rolling was 0.8g/cm 3 And obtaining the lithium ion battery negative plate.
Example 5
The embodiment provides a lithium ion battery negative plate, the lithium ion battery negative plate includes:
the mass percentage of the flaky porous hard carbon in the binary composite material is 10 percent, and the balance is nano silicon. The flaky porous hard carbon has a median particle diameter of 30 mu m, an aspect ratio of 1:100, an average pore diameter of 1000nm, a porosity of 70% and a specific surface area of 500m 2 And/g. The median particle diameter of the nano silicon is 1nm.
The preparation method of the flaky porous hard carbon comprises the following steps: heating and carbonizing polyvinyl chloride with a median particle size of 100 μm at 800 ℃ to obtain carbide; uniformly mixing 97% concentrated sulfuric acid and the obtained carbide according to a liquid-solid ratio of 2:1, and stripping the obtained carbide for 4 hours at 90 ℃ to obtain a stripped material; heating to 800 ℃, and pore-forming the obtained stripping material 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 ℃ to obtain carbide; uniformly mixing concentrated sulfuric acid and the obtained carbide according to a liquid-solid ratio of 1:2, and stripping the obtained carbide for 6 hours at 120 ℃ to obtain a stripped material; heating to 600 ℃, and pore-forming the obtained stripping material 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, active carbon, sodium carboxymethyl cellulose, polytetrafluoroethylene and lithium powder according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber, polyvinylidene fluoride and water with the mass of 60wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 10mg/cm 2 The compacted density after rolling is 1g/cm 3 And obtaining the lithium ion battery negative plate.
Example 6
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the median particle diameter of the phenolic resin when preparing the sheet-shaped porous hard carbon was 80. Mu.m.
Since the particle diameter of the phenolic resin was changed to 80. Mu.m, the median particle diameter of the prepared flaky porous hard carbon was 0.5. Mu.m.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 7
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the median particle diameter of the phenolic resin when preparing the sheet-shaped porous hard carbon was 300. Mu.m.
Since the particle diameter of the phenolic resin was changed to 300. Mu.m, the median particle diameter of the prepared flaky porous hard carbon was 35. Mu.m.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 8
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the peeling time for preparing the sheet-shaped porous hard carbon was 2 hours.
Since the peeling time is changed to 2h, the aspect ratio of the prepared flaky porous hard carbon is 1:2.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 9
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the peeling time for preparing the sheet-shaped porous hard carbon was 8 hours.
Since the exfoliation time was changed to 8 hours, the aspect ratio of the prepared flaky porous hard carbon was 1:110.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 10
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the temperature of the sheet-shaped porous hard carbon at which the temperature was raised was 500℃and the flow rate of oxygen was 100 mL/min.
The average pore diameter of the prepared flaky porous hard carbon is smaller than 10nm because the temperature of the heating is changed to 500 ℃ and the flow rate of oxygen is changed to 100 mL/min.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 11
The present example provided a lithium ion battery negative electrode sheet, and the conditions for preparing the sheet-shaped porous hard carbon were the same as those of example 1, except that the temperature of the sheet-shaped porous hard carbon at which the temperature was raised was 1000℃and the flow rate of oxygen was 500 mL/min.
As the temperature of the heating is changed to 1000 ℃ and the flow rate of oxygen is changed to 500mL/min, the average pore diameter of the prepared flaky porous hard carbon is more than 1000nm.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 12
The present example provides a lithium ion battery negative electrode sheet, and the composition content was the same as that of example 1 except that the median particle diameter of the nano silicon was 0.8 nm.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Example 13
The present example provides a lithium ion battery negative electrode sheet, and the composition content was the same as that of example 1 except that the median particle diameter of the nano silicon was 105 nm.
The composition of the other lithium ion battery negative plates in this example and the preparation method thereof are the same as those in example 1.
Comparative example 1
This comparative example provides a lithium ion battery negative electrode sheet, the lithium ion battery negative electrode sheet includes:
the flaky porous hard carbon has a median particle diameter of 20 mu m, an aspect ratio of 1:70, an average pore diameter of 600nm, a porosity of 50% and a specific surface area of 300m 2 And/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 amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber and water with the mass of 50wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 7mg/cm 2 The compacted density after rolling is 0.9g/cm 3 And obtaining the lithium ion battery negative plate.
Comparative example 2
This comparative example provides a lithium ion battery negative electrode sheet, the lithium ion battery negative electrode sheet includes:
the median particle diameter of the nano silicon is 80nm.
The preparation method of the lithium ion battery negative plate comprises the following steps: uniformly mixing nano silicon, conductive carbon black, lithium powder and sodium carboxymethyl cellulose according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber and water with the mass of 50wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 7mg/cm 2 The compacted density after rolling is 0.9g/cm 3 And 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 rest components of the lithium ion battery negative plate is the same as that of the example 1 except that 0.8 part of lithium powder is not contained in the lithium ion battery negative plate.
The preparation method of the flaky porous hard carbon of this comparative example 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, nano silicon, conductive carbon black and sodium carboxymethyl cellulose according to the formula amount to obtain mixed slurry; uniformly mixing the obtained mixed slurry, styrene-butadiene rubber and water with the mass of 50wt% of the mixed slurry to obtain negative electrode slurry; uniformly coating the obtained negative electrode slurry on a negative electrode current collector, wherein the surface density is 7mg/cm 2 The compacted density after rolling is 0.9g/cm 3 And obtaining the lithium ion battery negative plate.
Comparative example 4
This comparative example provides a lithium ion battery negative electrode sheet, the lithium ion battery negative electrode sheet includes:
the mass percentage of the common hard carbon in the binary composite material is 50 percent, and the balance is nano silicon; the median particle diameter of the conventional hard carbon was 20 μm, and the median particle diameter of the nano-silicon was 80nm.
The comparative example provides a preparation method of the common hard carbon, which comprises the following steps: and (3) heating and carbonizing the phenolic resin with the median particle size of 150 mu m at the temperature of 1000 ℃ to obtain the common hard carbon.
The preparation method of the lithium ion battery negative plate in the comparative example has the same steps and parameters as those in example 1 except that Kong Yingtan is replaced by conventional hard carbon.
The negative electrode sheets and the lithium sheets of the lithium ion batteries of examples 1-13 and comparative examples 1-4 were assembled into a CR2016 button half-cell for gram capacity measurement; the lithium ion battery negative plates and ternary materials of examples 1-13 and comparative examples 1-4 are assembled into a lithium ion full battery, performance measurement is carried out, the full battery is charged to an upper limit cutoff voltage at a constant current of 0.33 ℃, then is charged to 0.05 ℃ at a constant voltage, then is discharged to a lower limit cutoff voltage at a constant current of 0.33 ℃, and the first coulombic efficiency of the full battery is calculated; and (3) charging the full battery to an upper limit cutoff voltage at a constant current of 0.33 ℃, charging to 0.05 ℃ at a constant voltage, and disassembling the full battery to measure the expansion rate of the negative electrode plate. The full cell was charged to an upper limit cutoff voltage at a constant current of 0.5C, charged to 0.05C at a constant voltage, and then discharged to a lower limit cutoff voltage at a constant current of 0.5C, charged and discharged 100 times, and the discharge capacity ratio of the 100 th turn and the 1 st turn was recorded as a cyclic capacity retention rate, and the results are shown in table 1.
TABLE 1
From the data in table 1 the following conclusions can be drawn:
(1) According to the embodiment 1-5, the lithium ion battery negative plate provided by the invention has the advantages that the flaky porous hard carbon is compounded with the nano silicon-based material, 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, and the prepared lithium ion battery negative plate has high capacity, low expansion and high cycle capacity retention rate, overcomes the defects of single hard carbon and single silicon material, and has high first coulombic efficiency.
(2) As can be seen from comparison of examples 6 and 7 with example 1, when the median particle diameter of the flaky porous hard carbon is not within the preferred range provided by the invention, nano silicon cannot be well filled in the pore canal of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor cyclic capacity retention, which indicates that the median particle diameter range of the flaky porous hard carbon provided by the invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is beneficial to preparing the lithium ion battery with high capacity, low expansion and long cycle life.
(3) As can be seen from comparison of examples 8 and 9 with example 1, when the aspect ratio of the flaky porous hard carbon is not within the preferred range provided by the invention, nano silicon cannot be well filled in the pore canal of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor cyclic capacity retention, which indicates that the aspect ratio range of the flaky porous hard carbon provided by the invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is beneficial to preparing the lithium ion battery with high capacity, low expansion and long cycle life.
(4) As can be seen from comparison of examples 10 and 11 with example 1, when the average pore diameter of the flaky porous hard carbon is not within the preferred range provided by the invention, nano silicon cannot be well filled in the pore canal 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 invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is beneficial to preparing the lithium ion battery with high capacity, low expansion and high energy density.
(5) As can be seen from comparison of examples 12 and 13 with example 1, when the median particle diameter of the nano silicon is not within the preferred range provided by the invention, the nano silicon cannot be well filled in the pore canal of the hard carbon, so that the prepared lithium ion battery negative electrode sheet has high expansion rate, low capacity and poor cyclic capacity retention, which indicates that the median particle diameter range of the nano silicon provided by the invention is an important parameter of the hard carbon material in the lithium ion battery negative electrode sheet, and is beneficial to preparing the lithium ion battery with high capacity, low expansion and high energy density.
(6) As can be seen from comparison of comparative examples 1 and 2 with example 1, when the lithium ion battery negative electrode sheet does not combine hard carbon with nano silicon, the lithium ion battery prepared from the flaky porous hard carbon as the main raw material has low capacity, and the lithium ion battery prepared from the nano silicon has high expansion rate and poor cycle capacity retention, which indicates that the lithium ion battery negative electrode sheet provided by the invention overcomes the defect of hard carbon and nano silicon by combining the flaky porous hard carbon with the nano silicon, and the lithium ion battery with excellent performance of the composite material is prepared.
(7) As can be seen from comparison of comparative example 3 and example 1, when no lithium supplementing material is added to the lithium ion battery negative electrode sheet, the first coulombic efficiency of the prepared lithium ion battery is low, which indicates that the lithium supplementing material provided by the invention is an important material for preparing a hard carbon and nano silicon composite material lithium ion battery negative electrode sheet. The first coulomb efficiency of the composite lithium ion battery is improved by supplementing lithium to the negative electrode.
(8) As can be seen from comparison of comparative example 4 and example 1, when the conventional hard carbon material without a sheet-like pore canal is adopted, the prepared lithium ion battery has high expansion rate and poor cycle capacity retention, which indicates that the hard carbon material with a sheet-like porous property provided by the invention is an important property of a lithium ion battery negative plate, 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 electrode plate prepared by compounding the flaky porous hard carbon with 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 negative plate of the lithium ion battery is improved through lithium supplementation of the negative electrode. The nano silicon particles are dispersed in the pore canal of the hard carbon by regulating and controlling the particle diameter, the length-diameter ratio and the pore diameter of the flaky porous hard carbon and the particle diameter of the nano silicon-based particles. The pore canal limits the expansion of the nano silicon particles, so that the prepared lithium ion battery negative plate has high stability.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (14)

1. The lithium ion battery negative electrode plate is characterized by comprising 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
0.1-2 parts of lithium supplementing material;
the binary composite material is a composite material of flaky porous hard carbon and nano silicon-based material; the flaky porous hard carbon has large interlayer spacing and adjustable pore passages, the pore passages have a structure of through holes, and the nano silicon-based material is filled in the through holes; the aspect ratio of the flaky porous hard carbon is 1 (50-80); the average pore diameter of the flaky porous hard carbon is 400-800nm; the median particle diameter of the flaky porous hard carbon is 15-25 mu m; the median particle diameter of the nano silicon-based material is 70-90nm;
the binary composite material is prepared by mixing flaky porous hard carbon and a nano silicon-based material;
the flaky porous hard carbon is obtained by the following method: heating and carbonizing a hard carbon raw material to obtain carbide; uniformly mixing the obtained carbide with a stripping agent, and stripping for 4-6 hours at the temperature of 90-120 ℃ to obtain a stripped product; heating to 600-800 ℃ at the end temperature, aerating at the flow rate of 200-400mL/min, and pore-forming the obtained stripped substance to obtain the flaky porous hard carbon; the hard carbon raw material comprises any one or a combination of at least two of phenolic resin, epoxy resin, polystyrene or polyvinyl chloride.
2. The lithium ion battery negative plate according to claim 1, wherein the mass percentage of the flaky porous hard carbon in the binary composite material is 10-90wt% and the balance is the nano silicon-based material.
3. The lithium ion battery negative plate according to claim 2, wherein the mass percentage of the flaky porous hard carbon in the binary composite material is 40-80wt%.
4. The lithium ion battery negative electrode sheet according to claim 1, wherein the porosity of the sheet-shaped porous hard carbon is 30% -70%, and the specific surface area is 100-500m 2 /g。
5. The lithium ion battery negative electrode sheet according to claim 1, wherein the conductive agent comprises any one or a combination of at least two of conductive carbon black, graphite powder, or activated carbon.
6. The lithium ion battery negative electrode sheet according to claim 1, wherein the binder comprises any one or a combination of at least two of sodium carboxymethyl cellulose, styrene-butadiene rubber, polytetrafluoroethylene, or polyvinylidene fluoride.
7. The lithium ion battery negative electrode sheet according to claim 1, wherein the lithium supplementing material comprises lithium powder and/or lithium foil.
8. The lithium ion battery negative electrode sheet according to claim 1, wherein the hard carbon raw material has a median particle diameter of 100-200 μm.
9. The lithium ion battery negative electrode sheet according to claim 1, wherein the temperature of the heating carbonization is 800-1500 ℃.
10. The lithium ion battery negative electrode sheet according to claim 1, wherein the stripping agent comprises a saturated potassium hydroxide solution and/or concentrated sulfuric acid.
11. The negative electrode sheet for lithium ion batteries according to claim 1, wherein 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.
12. The lithium-ion battery negative electrode sheet of claim 1, wherein the vented gas comprises any one or a combination of at least two of oxygen, carbon dioxide, or water vapor.
13. A method for preparing a negative electrode sheet for a lithium ion battery according to any one of claims 1 to 12, comprising:
uniformly mixing binary composite material, conductive agent and lithium supplementing material with 40-60wt% adhesive to obtain mixed slurry;
uniformly mixing the obtained mixed slurry, a solvent and the balance of binder to obtain negative electrode slurry, wherein the solvent comprises water, and the mass of the solvent is 40-60wt% 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/cm 2 The compacted density of the rolling is 0.8-1.0g/cm 3 。
14. Use of a lithium ion battery negative electrode sheet according to any one of claims 1-12, characterized in that the lithium ion battery negative electrode sheet is used in a lithium ion battery.
CN202111120966.5A 2021-09-24 2021-09-24 Lithium ion battery negative plate and preparation method and application thereof Active CN113871574B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111120966.5A CN113871574B (en) 2021-09-24 2021-09-24 Lithium ion battery negative plate and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111120966.5A CN113871574B (en) 2021-09-24 2021-09-24 Lithium ion battery negative plate and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113871574A CN113871574A (en) 2021-12-31
CN113871574B true CN113871574B (en) 2023-08-08

Family

ID=78993796

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111120966.5A Active CN113871574B (en) 2021-09-24 2021-09-24 Lithium ion battery negative plate and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113871574B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114649505A (en) * 2022-04-07 2022-06-21 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery
CN115172654B (en) * 2022-07-25 2024-03-15 江苏正力新能电池技术有限公司 Lithium supplementing negative electrode plate and secondary battery

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162510A (en) * 1997-11-27 1999-06-18 Toray Ind Inc Nonaqueous electrolyte secondary battery
CN101916845A (en) * 2010-08-05 2010-12-15 深圳市贝特瑞新能源材料股份有限公司 Hard carbon material for power and energy-storage battery and preparation method thereof
WO2011157013A1 (en) * 2010-06-18 2011-12-22 深圳市贝特瑞新能源材料股份有限公司 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same
CN103311522A (en) * 2013-05-31 2013-09-18 中国科学院过程工程研究所 Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same
CN106898774A (en) * 2015-12-18 2017-06-27 中国科学院大连化学物理研究所 One kind peels off carbon block and its preparation and application
CN107123839A (en) * 2017-06-22 2017-09-01 宁波赛克雷特新能源科技有限公司 Method for extracting and separating electrolyte components and active materials from battery
CN108630912A (en) * 2018-03-11 2018-10-09 贵州格瑞特新材料有限公司 A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof
JP2018163776A (en) * 2017-03-24 2018-10-18 パナソニックＩｐマネジメント株式会社 Composite material and method of producing the same
CN109119601A (en) * 2018-06-11 2019-01-01 山西长韩新能源科技有限公司 Lithium ion secondary battery negative pole silico-carbo material and preparation method thereof, ion secondary battery cathode material lithium and lithium ion secondary battery
GB202012062D0 (en) * 2020-08-03 2020-09-16 Nexeon Ltd Electroactive materials for metal-ion batteries
CN112133915A (en) * 2020-08-13 2020-12-25 利普同呈(江苏)新能源科技有限公司 Preparation method of silicon-carbon composite material
WO2021179219A1 (en) * 2020-03-11 2021-09-16 宁德新能源科技有限公司 Anode plate and manufacturing method therefor, battery using anode plate, and electronic apparatus

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017175262A1 (en) * 2016-04-04 2017-10-12 テックワン株式会社 Carbon fiber, carbon fiber material production method, electrical device, and rechargeable battery
GB201818232D0 (en) * 2018-11-08 2018-12-26 Nexeon Ltd Electroactive materials for metal-ion batteries

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162510A (en) * 1997-11-27 1999-06-18 Toray Ind Inc Nonaqueous electrolyte secondary battery
WO2011157013A1 (en) * 2010-06-18 2011-12-22 深圳市贝特瑞新能源材料股份有限公司 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same
CN101916845A (en) * 2010-08-05 2010-12-15 深圳市贝特瑞新能源材料股份有限公司 Hard carbon material for power and energy-storage battery and preparation method thereof
CN103311522A (en) * 2013-05-31 2013-09-18 中国科学院过程工程研究所 Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same
CN106898774A (en) * 2015-12-18 2017-06-27 中国科学院大连化学物理研究所 One kind peels off carbon block and its preparation and application
JP2018163776A (en) * 2017-03-24 2018-10-18 パナソニックＩｐマネジメント株式会社 Composite material and method of producing the same
CN107123839A (en) * 2017-06-22 2017-09-01 宁波赛克雷特新能源科技有限公司 Method for extracting and separating electrolyte components and active materials from battery
CN108630912A (en) * 2018-03-11 2018-10-09 贵州格瑞特新材料有限公司 A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof
CN109119601A (en) * 2018-06-11 2019-01-01 山西长韩新能源科技有限公司 Lithium ion secondary battery negative pole silico-carbo material and preparation method thereof, ion secondary battery cathode material lithium and lithium ion secondary battery
WO2021179219A1 (en) * 2020-03-11 2021-09-16 宁德新能源科技有限公司 Anode plate and manufacturing method therefor, battery using anode plate, and electronic apparatus
GB202012062D0 (en) * 2020-08-03 2020-09-16 Nexeon Ltd Electroactive materials for metal-ion batteries
CN112133915A (en) * 2020-08-13 2020-12-25 利普同呈(江苏)新能源科技有限公司 Preparation method of silicon-carbon composite material

Also Published As

Publication number Publication date
CN113871574A (en) 2021-12-31

Similar Documents

Publication Publication Date Title
Jiang et al. Honeycomb-like nitrogen and sulfur dual-doped hierarchical porous biomass carbon bifunctional interlayer for advanced lithium-sulfur batteries
EP3133690A1 (en) Silicon-carbon composite particulate material
JP2022507401A (en) Silicon-Carbon Composite Anode Material
CN112467108B (en) Porous silica composite material and preparation method and application thereof
CN112002883A (en) Silicon-based composite material for negative electrode active material, negative electrode plate and lithium ion battery
WO2014032595A1 (en) Negative electrode material, method for producing the same, negative electrode, and battery comprising the same
Al Ja’farawy et al. A review: the development of SiO 2/C anode materials for lithium-ion batteries
CN102694155A (en) Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same
CN113871574B (en) Lithium ion battery negative plate and preparation method and application thereof
CN113659125B (en) Silicon-carbon composite material and preparation method thereof
CN111342031B (en) Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN112687843A (en) Composite conductive agent suitable for silicon-based negative electrode, preparation method of silicon-based negative electrode and lithium ion battery
CN111446431A (en) Method for enhancing interface contact of silicon-oxygen-carbon cathode material of lithium ion battery through oxygen transfer reaction
CN113851627A (en) Porous silicon-carbon negative electrode material and preparation method thereof
WO2020067609A1 (en) Anode active material for lithium secondary battery and lithium secondary battery comprising same
CN108134087A (en) Negative material and preparation method thereof used in a kind of lithium-ion-power cell
Venugopal et al. A facile synthetic route for Co 3 O 4 nanoparticle/porous carbon composite as an efficient anode material for lithium-ion batteries
CN113555541A (en) High-energy-density lithium ion battery
CN108461753B (en) Carbon nanotube conductive agent slurry for lithium ion battery cathode material and preparation method thereof
CN110299511B (en) Nano composite negative plate, preparation method thereof and lithium ion battery
CN108110235B (en) Hollow nickel-nickel oxide nanoparticle/porous carbon nanosheet layer composite material and preparation method and application thereof
CN115810737A (en) Sodium ion battery positive electrode material, preparation method, battery and electric equipment
CN116154105A (en) Micron silicon negative electrode, preparation method thereof and lithium ion battery
Liu et al. Phenolic resin-coated porous silicon/carbon microspheres anode materials for lithium-ion batteries
CN114105133A (en) Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant