CN112382794A - Preparation method of graphite cathode lithium ion battery - Google Patents

Preparation method of graphite cathode lithium ion battery Download PDF

Info

Publication number
CN112382794A
CN112382794A CN202010767197.7A CN202010767197A CN112382794A CN 112382794 A CN112382794 A CN 112382794A CN 202010767197 A CN202010767197 A CN 202010767197A CN 112382794 A CN112382794 A CN 112382794A
Authority
CN
China
Prior art keywords
lithium ion
negative
ion battery
negative electrode
graphite
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.)
Granted
Application number
CN202010767197.7A
Other languages
Chinese (zh)
Other versions
CN112382794B (en
Inventor
杨亦双
陈阳
韩笑
李凡群
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.)
Wanxiang A123 Systems Asia Co Ltd
Original Assignee
Wanxiang Group Corp
Wanxiang A123 Systems Asia 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 Wanxiang Group Corp, Wanxiang A123 Systems Asia Co Ltd filed Critical Wanxiang Group Corp
Priority to CN202010767197.7A priority Critical patent/CN112382794B/en
Publication of CN112382794A publication Critical patent/CN112382794A/en
Application granted granted Critical
Publication of CN112382794B publication Critical patent/CN112382794B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a graphite cathode lithium ion battery, which comprises the following steps: (1) preparation of negative active material: A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at constant temperature for reaction, and cooling to obtain modified asphalt; B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction to obtain a coated product; C) carbonizing and cooling the coated product to obtain a negative active material; (2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode sheet; (3) and (6) assembling the battery. According to the invention, the surface of the graphite negative electrode is coated with a certain amount of amorphous carbon, so that the interface between the electrolyte and the graphite is improved, the dynamic performance of lithium ions on the graphite surface is improved, a negative electrode plate with complete lithium intercalation is obtained, and the rate capability of the battery is improved.

Description

Preparation method of graphite cathode lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a graphite cathode lithium ion battery.
Background
The energy density of lithium ion batteries depends to a large extent on the negative electrode material, and from the commercialization of lithium ion batteries to the present, the most mature and widely used negative electrode material is carbon material, and most of the negative electrode material is still graphite. For example, a chinese patent publication No. CN101106191 discloses a method for preparing a composite graphite negative electrode material and a lithium ion battery using the same, in which the method for preparing the composite graphite negative electrode material is as follows: firstly, synthesizing graphite into Graphite Intercalation Compounds (GICs), then coating the GICs with a soft carbon precursor, carrying out heat treatment in an oxygen-isolated atmosphere at 700-3000 ℃, and sieving to obtain the composite graphite cathode material. The lithium ion battery prepared by using the composite graphite cathode material has the advantages of low initial irreversible capacity, good high-current charge and discharge performance, high capacity, long cycle life and the like.
Although graphite has very considerable electrochemical performance when being used as a lithium battery cathode material, the graphite has poor stability of a layered structure and is easy to collapse after long-time charge and discharge cycles, so that the specific capacity is seriously reduced and the energy storage life is greatly shortened; along with the increase of the graphitization degree, the lithium embedding difficulty is increased, the multiplying power performance of the battery is poor, and the battery cannot be charged and discharged by large current, otherwise, the battery can be damaged.
Disclosure of Invention
The invention aims to overcome the defects that when graphite is used as a negative electrode material of a lithium ion battery in the prior art, the graphite laminated structure has poor stability and is easy to collapse after long-time charge-discharge circulation, so that the specific capacity is seriously reduced and the energy storage life is greatly shortened; and along with the improvement of graphitization degree, the difficulty of lithium intercalation is improved, and the multiplying power performance of the battery is poorer, the preparation method of the graphite cathode lithium ion battery is provided, and the dynamic performance of lithium ions on the graphite surface is improved by coating a certain amount of amorphous carbon on the surface of the artificial graphite cathode, so that a cathode plate with complete lithium intercalation is obtained, and the multiplying power performance of the battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at a constant temperature for reacting for 2-3 hours, and cooling to obtain modified asphalt;
B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction for 1-2 hours at the temperature of 300-400 ℃ to obtain a coated product;
C) carbonizing the coated product at 700-1000 ℃ in a nitrogen atmosphere for 2-3 h, and cooling to room temperature to obtain the negative active material;
(2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
(3) assembling the battery: and assembling the prepared negative plate and the positive plate together by adopting a diaphragm for liquid injection, and forming to obtain the graphite negative lithium ion battery.
When the negative electrode active material is prepared, the modified asphalt is used for coating the needle coke powder, so that the surface of the artificial graphite is coated with a layer of uniform amorphous carbon, the artificial graphite with high graphitization degree is prevented from being in direct contact with electrolyte, the graphite laminated structure is prevented from being damaged, and the negative electrode plate with uniform and complete lithium intercalation is obtained; meanwhile, the amorphous carbon can improve the dynamic performance of lithium ions on the surface of graphite, solve the lithium intercalation defect in the formation process, and reduce the direct current impedance of the battery, thereby improving the rate capability of the battery.
Meanwhile, when the negative active material is prepared, the ethylene-vinyl acetate copolymer is used for modifying the asphalt under the action of the cross-linking agent and the catalyst in the step A), so that the softening point of the asphalt is improved, the content of light components in the asphalt is reduced, the gas overflow in the carbonization process is reduced, a compact amorphous carbon layer can be formed on the surface of the graphite after carbonization, the formation of defects such as cracks, holes and the like is avoided, the contact between the graphite and the electrolyte is further reduced, and the irreversible capacity in the first charge-discharge process is reduced. The addition of the cross-linking agent can improve the stability of the modified asphalt through the cross-linking effect and avoid the phase separation of the modified asphalt.
Preferably, the adding amount of the ethylene-vinyl acetate copolymer, the cross-linking agent and the catalyst in the step A) is 2-4%, 0.8-1.2% and 2-3% of the mass of the asphalt respectively.
Preferably, the crosslinking agent in step A) is divinylbenzene and the catalyst is p-toluenesulfonic acid.
Preferably, the modified asphalt and the needle-shaped coke powder in the step B) respectively account for 0.6-2.0% and 98.0-99.4% of the total mass of the mixture after the modified asphalt and the needle-shaped coke powder are mixed.
Preferably, the space velocity in the carbonization in the step C) is 0.5-1 m/min. The space velocity during carbonization can change the pore channel structure of the amorphous carbon layer on the surface of the graphite and the amorphous degree of the carbon layer, and the space velocity is within the range of the invention, so that the carbon skeleton of the amorphous carbon layer can be more ordered while the pore channel is left, thereby improving the electrochemical performance of the amorphous carbon layer.
Preferably, the negative electrode slurry in the step (2) comprises 96-98 parts by weight of a negative electrode material, 0.5-1 part by weight of a conductive agent, 0-1 part by weight of a thickening agent, 1-2 parts by weight of a binder and 60-250 parts by weight of a solvent.
Preferably, the preparation method of the binder in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction container according to the mass ratio of (1-3) to (1-3), and then adding the mixture according to the molar ratio of (2-3): 5, reacting potassium persulfate and sodium bisulfite at the temperature of 90-100 ℃ for 4-6 h to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3-3.5% of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g (10-15 mL) to 0.03-0.05 g, introducing chlorine gas at 90-140 ℃ for reaction for 1-6 h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1.0-2.5 mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g (10-15 mL), reacting at 60-90 ℃ for 30-60 min, and removing the solvent to obtain the binder.
In the preparation process of the binder, firstly, the lithium acrylate-acrylamide-acrylonitrile copolymer is prepared through the step a), and hydrophilic units-CH exist in the lithium acrylate-acrylamide-acrylonitrile copolymer at the same time2CH(COO-)-、-CH2CH(CONH2) -, and the lipophilic unit-CH2Ch (cn) -, since the surface of the negative active material is hydrophobic, the lipophilic unit in the binder has a comparable affinity with the negative active material, and can improve the dispersion of the negative active material in water to achieve good stability of the negative paste and can provide a binding force with the negative active material; meanwhile, the hydrophilic groups on the binder can form hydrogen bonds with the surface of the copper foil, so that the binder and the current collector have good binding power. In summary, the binder used in the present invention can play a role in both binding in the negative electrode sheet and in the negative electrode slurryThe suspending effect is achieved, so that the binder can reduce the proportion of the thickening agent and the binder in the negative electrode slurry; in addition, because the binder is a straight-chain polymer, branched chain crosslinking cannot occur, and the polymer cannot be dissolved in water, the solution formed by dissolving the binder in water is easier to form a film on the surface of the negative electrode active material, the solution has a larger contact area with the negative electrode active material, more binding points are formed, the binding property of the solution is improved, the intertwined polymer chains additionally provide part of binding property, the use amount of the binder in the negative electrode slurry can be further reduced by enhancing the binding effect of the binder, the proportion of the negative electrode active material is improved, and the electrochemical performance of the battery is improved.
Meanwhile, the lithium acrylate-acrylamide-acrylonitrile copolymer is subjected to halogenation reaction and elimination reaction to form conjugated double bonds through the steps b) and c), and the formation of the conjugated double bonds can increase the electronic conductivity of the binder, so that the internal resistance of the battery is reduced, and the rate capability is improved; in addition, the increase of the electron conductivity of the binder can further reduce the amount of the conductive agent in the anode slurry, thereby increasing the proportion of the anode active material.
Preferably, the conductive agent in the step (2) is at least one of conductive carbon black, single-walled carbon nanotube and nano carbon fiber; the thickening agent is sodium carboxymethyl cellulose; the solvent is water.
Preferably, the positive electrode active material of the positive electrode plate in the step (3) is a nickel-cobalt-manganese ternary material.
Preferably, the separator in step (3) is a PP or PE based separator; the electrolyte during liquid injection is lithium hexafluorophosphate electrolyte.
Therefore, the invention has the following beneficial effects:
(1) when the negative electrode active material is prepared, the surface of the artificial graphite is coated with a layer of uniform amorphous carbon, so that the artificial graphite with high graphitization degree is prevented from being directly contacted with electrolyte, the damage of a graphite laminated structure is further avoided, and a negative electrode plate with uniform and complete lithium intercalation is obtained; meanwhile, the amorphous carbon can improve the dynamic performance of lithium ions on the surface of graphite, solve the lithium intercalation defect in the formation process and reduce the direct current impedance of the battery, thereby improving the rate capability of the battery;
(2) the ethylene-vinyl acetate copolymer is used for modifying the asphalt, so that the softening point of the asphalt is improved, and the content of light components in the asphalt is reduced, so that the overflow of gas in the carbonization process is reduced, a compact amorphous carbon layer can be formed on the surface of the graphite after carbonization, and the formation of defects such as cracks, holes and the like is avoided;
(3) the negative electrode binder adopts lithium acrylate-acrylamide-acrylonitrile copolymer which forms conjugated double bonds through halogenation reaction and elimination reaction, so that the binder can play a role in binding in a negative electrode sheet and playing a role in suspending in negative electrode slurry, the proportion of a thickening agent and the binder in the negative electrode slurry is reduced, the proportion of a negative electrode active substance is improved, the electronic conductivity of the binder can be increased, the internal resistance of a battery is reduced, and the electrochemical performance of the battery is improved.
Drawings
Fig. 1 is a picture of a negative electrode sheet after the cycle test of example 1.
Fig. 2 is a picture of the negative electrode sheet after the cycle test of comparative example 1.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 2:1:2, adding potassium persulfate and sodium bisulfite with the molar ratio of 1:2, and reacting at 95 ℃ for 5 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.2 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:12mL:0.04g, introducing chlorine gas at 110 ℃ for reaction for 4h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 2mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:12mL, reacting at 75 ℃ for 40min, and removing the solvent to obtain the binder.
Example 2:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 140 ℃, adding an ethylene-vinyl acetate copolymer accounting for 2% of the mass of the asphalt powder, 0.8% of divinylbenzene and 2% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2 hours, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 0.6 percent of the total mass of the mixture, the needle coke powder accounts for 99.4 percent of the total mass of the mixture, and performing coating reaction at 300 ℃ for 2 hours to obtain a coated product;
C) carbonizing the coated product at 700 ℃ under nitrogen atmosphere at an airspeed of 0.5m/min for 3h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 96 parts by weight of negative active material, 0.5 part by weight of Super P and 2 parts by weight of binder into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 1:1:3, adding potassium persulfate and sodium bisulfite with the molar ratio of 2:5, and reacting at 90 ℃ for 6 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:10mL:0.03g, introducing chlorine gas at 90 ℃ for reacting for 6h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:10mL, reacting at 60 ℃ for 60min, and removing the solvent to obtain the binder.
Example 3:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 150 ℃, adding an ethylene-vinyl acetate copolymer accounting for 4% of the mass of the asphalt powder, 1.2% of divinylbenzene and 3% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 3 hours, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 2% of the total mass of the mixture, the needle-shaped coke powder accounts for 98% of the total mass of the mixture, and performing coating reaction at 400 ℃ for 1 hour to obtain a coated product;
C) carbonizing the coated product at 1000 ℃ under nitrogen atmosphere at an airspeed of 1m/min for 2h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 98 parts by weight of negative electrode active material, 1 part by weight of SWCNT, 1 part by weight of binder and 1 part by weight of sodium carboxymethylcellulose into deionized water, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PE-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 3:1:1, adding potassium persulfate and sodium bisulfite with the molar ratio of 3:5, and reacting at 100 ℃ for 4 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.5 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:15mL:0.05g, introducing chlorine gas at 140 ℃ for reaction for 1h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 2.5mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:15mL, reacting at 90 ℃ for 30min, and removing the solvent to obtain the binder.
Comparative example 1:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material: needle-shaped coke powder is adopted as a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Wherein the binder in the step (2) is prepared by the same method as in example 1.
Comparative example 2:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) mixing asphalt powder and needle coke powder, adding the mixture into a coating reaction kettle, wherein the asphalt powder accounts for 1% of the total mass of the mixture, the needle coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
B) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Wherein the binder in the step (2) is prepared by the same method as in example 1.
Comparative example 3:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of styrene butadiene rubber and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Comparative example 4:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps: adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 2:1:2, adding potassium persulfate and sodium bisulfite with the molar ratio of 1:2, and reacting at 95 ℃ for 5 hours to obtain the binder; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.2 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile.
The peel strength of the negative electrode sheets and the performance of the lithium ion batteries manufactured in example 1 and comparative example 1 were measured, and the results are shown in table 1.
Table 1: and testing the performance of the negative plate and the lithium ion battery.
Figure BDA0002615150060000081
As can be seen from table 1, the lithium ion batteries prepared by the method in embodiments 1 to 3 have high peel strength and high capacity of the negative electrode sheet, and good cyclic charge-discharge performance and rate capability of the batteries; in the comparative example 1, the graphite is not coated by using asphalt, so that the cyclic charge and discharge performance and the rate capability of the battery are obviously reduced compared with those in the example 1; in comparative example 2, the asphalt was not modified, and the performance of the battery was also reduced as compared with that in example 1; in comparative example 3, the binder of the present invention was not used, but the conventional styrene butadiene rubber was used as the binder, and the peel strength of the negative electrode sheet was significantly reduced, and the battery performance was decreased; in the preparation of the binder in comparative example 4, the lithium acrylate-acrylamide-acrylonitrile copolymer was not subjected to subsequent modification, and the battery performance was also reduced as compared with that in example 1; as can be seen from fig. 1 and 2, the cycled surface of the negative electrode sheet in example 1 was uniform and no black spots appeared, whereas the cycled surface of the negative electrode sheet in comparative example 1 had more noticeable black spots. The method provided by the invention is proved to be capable of effectively improving the cycle charge and discharge performance and the rate capability of the lithium ion battery.

Claims (10)

1. A preparation method of a graphite cathode lithium ion battery is characterized by comprising the following steps:
(1) preparation of negative active material:
A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at a constant temperature for reacting for 2-3 hours, and cooling to obtain modified asphalt;
B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction for 1-2 hours at the temperature of 300-400 ℃ to obtain a coated product;
C) carbonizing the coated product at 700-1000 ℃ in a nitrogen atmosphere for 2-3 h, and cooling to room temperature to obtain the negative active material;
(2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
(3) assembling the battery: and assembling the prepared negative plate and the positive plate together by adopting a diaphragm for liquid injection, and forming to obtain the graphite negative lithium ion battery.
2. The preparation method of the graphite cathode lithium ion battery as claimed in claim 1, wherein the addition amounts of the ethylene-vinyl acetate copolymer, the crosslinking agent and the catalyst in the step A) are respectively 2-4%, 0.8-1.2% and 2-3% of the mass of the asphalt.
3. The method for preparing the graphite cathode lithium ion battery as claimed in claim 1 or 2, wherein the cross-linking agent in the step A) is divinylbenzene, and the catalyst is p-toluenesulfonic acid.
4. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the modified asphalt and the needle-shaped coke powder in the step B) respectively account for 0.6-2.0% and 98.0-99.4% of the total mass of the mixture after mixing the modified asphalt and the needle-shaped coke powder.
5. The preparation method of the graphite cathode lithium ion battery as claimed in claim 1, wherein the space velocity during carbonization in the step C) is 0.5-1 m/min.
6. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the cathode slurry in the step (2) comprises 96-98 parts by weight of cathode material, 0.5-1 part by weight of conductive agent, 0-1 part by weight of thickening agent, 1-2 parts by weight of binder and 60-250 parts by weight of solvent.
7. The method for preparing a graphite cathode lithium ion battery according to claim 1 or 6, wherein the binder preparation method in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction container according to the mass ratio of (1-3) to (1-3), and then adding the mixture according to the molar ratio of (2-3): 5, reacting potassium persulfate and sodium bisulfite at the temperature of 90-100 ℃ for 4-6 h to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3-3.5% of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g (10-15 mL) to 0.03-0.05 g, introducing chlorine gas at 90-140 ℃ for reaction for 1-6 h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1.0-2.5 mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g (10-15 mL), reacting at 60-90 ℃ for 30-60 min, and removing the solvent to obtain the binder.
8. The method for preparing a graphite cathode lithium ion battery according to claim 1 or 6, wherein the conductive agent in the step (2) is at least one of conductive carbon black, single-walled carbon nanotube and carbon nanofiber; the thickening agent is sodium carboxymethyl cellulose; the solvent is water.
9. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the cathode active material of the cathode plate in the step (3) is a nickel-cobalt-manganese ternary material.
10. The method for preparing the graphite cathode lithium ion battery according to claim 1, wherein the separator in the step (3) is a PP or PE-based separator; the electrolyte during liquid injection is lithium hexafluorophosphate electrolyte.
CN202010767197.7A 2020-08-03 2020-08-03 Preparation method of graphite cathode lithium ion battery Active CN112382794B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010767197.7A CN112382794B (en) 2020-08-03 2020-08-03 Preparation method of graphite cathode lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010767197.7A CN112382794B (en) 2020-08-03 2020-08-03 Preparation method of graphite cathode lithium ion battery

Publications (2)

Publication Number Publication Date
CN112382794A true CN112382794A (en) 2021-02-19
CN112382794B CN112382794B (en) 2021-10-15

Family

ID=74586382

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010767197.7A Active CN112382794B (en) 2020-08-03 2020-08-03 Preparation method of graphite cathode lithium ion battery

Country Status (1)

Country Link
CN (1) CN112382794B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097429A (en) * 2021-03-30 2021-07-09 宁德新能源科技有限公司 Electrochemical device and electronic apparatus
CN113991076A (en) * 2021-09-30 2022-01-28 湖州凯金新能源科技有限公司 Long-cycle negative electrode material and preparation method thereof
CN113991077A (en) * 2021-09-30 2022-01-28 湖州凯金新能源科技有限公司 Graphite composite material for lithium battery and preparation method thereof
CN114566649A (en) * 2022-02-24 2022-05-31 东莞赣锋电子有限公司 High-surface-density negative plate and preparation method thereof
CN114725323A (en) * 2022-05-16 2022-07-08 湖北亿纬动力有限公司 Preparation method and application of negative pole piece
CN114784274A (en) * 2022-04-07 2022-07-22 陕西科技大学 Biomass material modified polymer binder, preparation method thereof and application thereof in silicon-based negative electrode of lithium ion battery
CN115064697A (en) * 2022-07-14 2022-09-16 中国科学院山西煤炭化学研究所 Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery
CN115974065A (en) * 2022-12-06 2023-04-18 昆明理工大学 Method for preparing hard carbon material based on aromatized petroleum asphalt and application thereof
CN116666612A (en) * 2023-08-01 2023-08-29 江苏正力新能电池技术有限公司 Negative electrode material and application thereof in sodium ion secondary battery
CN117945391A (en) * 2024-03-27 2024-04-30 太原理工大学 Asphalt-based carbon material and preparation method and application thereof
CN118062838A (en) * 2024-02-22 2024-05-24 深圳市贝特瑞新能源技术研究院有限公司 Graphite negative electrode material, preparation method thereof, lithium ion battery and electric equipment

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101717587A (en) * 2009-12-15 2010-06-02 西安理工大学 Blended composite modified asphalt and preparation method thereof
CN101864019A (en) * 2010-05-13 2010-10-20 上海现代药物制剂工程研究中心有限公司 Preparation method of sodium polystyrene sulfonate ion exchange resin
CN102332600A (en) * 2010-12-17 2012-01-25 东莞新能源科技有限公司 Lithium ion battery
CN102535304A (en) * 2012-03-19 2012-07-04 交通运输部公路科学研究所 Crack pressing tape for cracks of asphalt road surface and preparation method of crack pressing tape
CN103151513A (en) * 2013-03-13 2013-06-12 山东神工海特电子科技有限公司 High-performance ternary power battery and preparation method of high-performance ternary power battery
CN103956450A (en) * 2014-05-16 2014-07-30 中国东方电气集团有限公司 Composite membrane for lithium ion batteries and preparation method thereof
CN105018001A (en) * 2014-04-28 2015-11-04 成都中科来方能源科技有限公司 Aqueous binder used for lithium ion batteries, positive and negative electrode plates and coating membrane
CN206864542U (en) * 2017-06-22 2018-01-09 北京圣比和科技有限公司 A kind of 3V level lithium ion batteries based on lithium titanate anode material
CN108541237A (en) * 2015-04-01 2018-09-14 3M创新有限公司 Multi-layer product including adherent surfaces and its method
US20180291531A1 (en) * 2015-09-25 2018-10-11 China Petroleum & Chemical Corporation Electroconductive polymer fiber and its preparation method and application
EP3396750A1 (en) * 2015-12-24 2018-10-31 LG Chem, Ltd. Binder composition for secondary battery, and electrode for secondary battery and lithium secondary battery comprising same
CN108832125A (en) * 2018-05-28 2018-11-16 九江华先新材料有限公司 A kind of cathode of lithium battery aqueous binders and preparation method, electrode piece preparation method
CN109338727A (en) * 2018-09-26 2019-02-15 嘉兴学院 A kind of preparation method of flexible wearable strain transducer
CN109860524A (en) * 2017-11-30 2019-06-07 宝武炭材料科技有限公司 A kind of method of solid asphalt low temperature cladding preparation negative electrode material
EP3502151A1 (en) * 2016-08-17 2019-06-26 Sichuan Indigo Technology Co., Ltd. Acrylonitrile copolymer adhesive and use of same in lithium ion battery
CN110982008A (en) * 2019-12-30 2020-04-10 宣城研一新能源科技有限公司 Aqueous binder for negative electrode of lithium ion battery
CN111139002A (en) * 2019-12-30 2020-05-12 宣城研一新能源科技有限公司 Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101717587A (en) * 2009-12-15 2010-06-02 西安理工大学 Blended composite modified asphalt and preparation method thereof
CN101864019A (en) * 2010-05-13 2010-10-20 上海现代药物制剂工程研究中心有限公司 Preparation method of sodium polystyrene sulfonate ion exchange resin
CN102332600A (en) * 2010-12-17 2012-01-25 东莞新能源科技有限公司 Lithium ion battery
CN102535304A (en) * 2012-03-19 2012-07-04 交通运输部公路科学研究所 Crack pressing tape for cracks of asphalt road surface and preparation method of crack pressing tape
CN103151513A (en) * 2013-03-13 2013-06-12 山东神工海特电子科技有限公司 High-performance ternary power battery and preparation method of high-performance ternary power battery
CN105018001A (en) * 2014-04-28 2015-11-04 成都中科来方能源科技有限公司 Aqueous binder used for lithium ion batteries, positive and negative electrode plates and coating membrane
CN103956450A (en) * 2014-05-16 2014-07-30 中国东方电气集团有限公司 Composite membrane for lithium ion batteries and preparation method thereof
CN108541237A (en) * 2015-04-01 2018-09-14 3M创新有限公司 Multi-layer product including adherent surfaces and its method
US20180291531A1 (en) * 2015-09-25 2018-10-11 China Petroleum & Chemical Corporation Electroconductive polymer fiber and its preparation method and application
EP3396750A1 (en) * 2015-12-24 2018-10-31 LG Chem, Ltd. Binder composition for secondary battery, and electrode for secondary battery and lithium secondary battery comprising same
EP3502151A1 (en) * 2016-08-17 2019-06-26 Sichuan Indigo Technology Co., Ltd. Acrylonitrile copolymer adhesive and use of same in lithium ion battery
CN206864542U (en) * 2017-06-22 2018-01-09 北京圣比和科技有限公司 A kind of 3V level lithium ion batteries based on lithium titanate anode material
CN109860524A (en) * 2017-11-30 2019-06-07 宝武炭材料科技有限公司 A kind of method of solid asphalt low temperature cladding preparation negative electrode material
CN108832125A (en) * 2018-05-28 2018-11-16 九江华先新材料有限公司 A kind of cathode of lithium battery aqueous binders and preparation method, electrode piece preparation method
CN109338727A (en) * 2018-09-26 2019-02-15 嘉兴学院 A kind of preparation method of flexible wearable strain transducer
CN110982008A (en) * 2019-12-30 2020-04-10 宣城研一新能源科技有限公司 Aqueous binder for negative electrode of lithium ion battery
CN111139002A (en) * 2019-12-30 2020-05-12 宣城研一新能源科技有限公司 Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097429A (en) * 2021-03-30 2021-07-09 宁德新能源科技有限公司 Electrochemical device and electronic apparatus
CN113991076B (en) * 2021-09-30 2023-07-28 湖州凯金新能源科技有限公司 Long-cycle anode material and preparation method thereof
CN113991076A (en) * 2021-09-30 2022-01-28 湖州凯金新能源科技有限公司 Long-cycle negative electrode material and preparation method thereof
CN113991077A (en) * 2021-09-30 2022-01-28 湖州凯金新能源科技有限公司 Graphite composite material for lithium battery and preparation method thereof
CN113991077B (en) * 2021-09-30 2023-08-04 湖州凯金新能源科技有限公司 Graphite composite material for lithium battery and preparation method thereof
CN114566649A (en) * 2022-02-24 2022-05-31 东莞赣锋电子有限公司 High-surface-density negative plate and preparation method thereof
CN114566649B (en) * 2022-02-24 2024-01-23 东莞赣锋电子有限公司 High-areal-density negative plate and preparation method thereof
CN114784274A (en) * 2022-04-07 2022-07-22 陕西科技大学 Biomass material modified polymer binder, preparation method thereof and application thereof in silicon-based negative electrode of lithium ion battery
CN114725323A (en) * 2022-05-16 2022-07-08 湖北亿纬动力有限公司 Preparation method and application of negative pole piece
CN114725323B (en) * 2022-05-16 2024-04-02 湖北亿纬动力有限公司 Preparation method and application of negative electrode plate
CN115064697A (en) * 2022-07-14 2022-09-16 中国科学院山西煤炭化学研究所 Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery
CN115064697B (en) * 2022-07-14 2024-08-23 中国科学院山西煤炭化学研究所 Application of modified polyacrylonitrile, binder, negative plate and lithium ion battery
CN115974065A (en) * 2022-12-06 2023-04-18 昆明理工大学 Method for preparing hard carbon material based on aromatized petroleum asphalt and application thereof
CN115974065B (en) * 2022-12-06 2023-09-22 昆明理工大学 Method for preparing hard carbon material based on aromatized petroleum asphalt and application thereof
CN116666612A (en) * 2023-08-01 2023-08-29 江苏正力新能电池技术有限公司 Negative electrode material and application thereof in sodium ion secondary battery
CN116666612B (en) * 2023-08-01 2023-09-29 江苏正力新能电池技术有限公司 Negative electrode material and application thereof in sodium ion secondary battery
CN118062838A (en) * 2024-02-22 2024-05-24 深圳市贝特瑞新能源技术研究院有限公司 Graphite negative electrode material, preparation method thereof, lithium ion battery and electric equipment
CN117945391A (en) * 2024-03-27 2024-04-30 太原理工大学 Asphalt-based carbon material and preparation method and application thereof

Also Published As

Publication number Publication date
CN112382794B (en) 2021-10-15

Similar Documents

Publication Publication Date Title
CN112382794B (en) Preparation method of graphite cathode lithium ion battery
CN109103399B (en) Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery
CN111293312B (en) Flexible multifunctional crosslinking adhesive and preparation method and application thereof
CN109935784A (en) Positive plate and electrochemical cell
CN108306006A (en) Negative material, negative plate and preparation method thereof, lithium ion battery and preparation method thereof
CN110190284B (en) Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof
CN109524653A (en) A method of lithium-ion capacitor specific capacity is promoted using conducting polymer
CN112331830A (en) Preparation method of graphene-coated nickel-cobalt-manganese ternary positive electrode material
CN115360344B (en) Composite positive electrode material for sodium ion battery and preparation method thereof
CN113555541A (en) High-energy-density lithium ion battery
CN116111091A (en) Adhesive composition, sodium ion battery positive electrode slurry and sodium ion battery
CN114400297A (en) Lithium ion battery composite pole piece containing aerogel coating and preparation method thereof
CN107742697B (en) Preparation method of external application type lead-carbon battery cathode
CN116826030B (en) Composite positive electrode material based on small molecular organic matters and manufacturing method thereof
CN113555540A (en) Fast-charging polymer lithium ion battery
CN112928233A (en) Preparation method and application of NiO-C composite electrode material with core-shell structure
CN109713247A (en) Ion doping, nickel-cobalt lithium manganate cathode material of in-stiu coating and preparation method thereof
CN115341309A (en) Porous silver-doped hard carbon composite material and preparation method and application thereof
CN114772582A (en) Composite carbon material and application thereof in lithium ion battery
CN109994723A (en) A kind of SiOxThe preparation method of-G/PAA-PANi/Cu composite material
CN112366349B (en) Method for prolonging high-rate cycle life of high-nickel ternary lithium ion battery
CN111415823B (en) Ni-Sn-S composite material and preparation method and application thereof
CN115692623B (en) Lithium ion battery negative plate, preparation method thereof and lithium ion battery
CN114551844B (en) Lithium titanate composite negative electrode material and preparation method thereof
CN114122316B (en) Negative electrode and use 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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20211108

Address after: No.855, Jianshe 2nd Road, Xiaoshan Economic and Technological Development Zone, Hangzhou City, Zhejiang Province

Patentee after: Wanxiang A123 Co.,Ltd.

Address before: No.855 Jianshe Er Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province

Patentee before: Wanxiang A123 Co.,Ltd.

Patentee before: WANXIANG GROUP Co.,Ltd.