CN111139002B - Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery - Google Patents
Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery Download PDFInfo
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- CN111139002B CN111139002B CN201911394759.1A CN201911394759A CN111139002B CN 111139002 B CN111139002 B CN 111139002B CN 201911394759 A CN201911394759 A CN 201911394759A CN 111139002 B CN111139002 B CN 111139002B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
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- 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
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- 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
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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 discloses a water-soluble adhesive for a lithium ion battery, a preparation method of the water-soluble adhesive, an electrode plate and a battery, and aims to solve the technical problems of improving the high-temperature storage and high-temperature cycle performance of the lithium ion battery and reducing the cost. The invention relates to a water-soluble adhesive for a lithium ion battery, which comprises the following components in percentage by mass: the monomer of formula 1 is 5-75%, the monomer of formula 2 is 1-35%, the monomer of formula 3 is 5-65%, and a multi-component copolymer is formed. The method comprises the steps of mixing a monomer shown in a formula 1, a monomer shown in a formula 2 and a monomer shown in a formula 3 to obtain a solution, adding an initiator to obtain a polymerization product, and neutralizing with an aqueous alkali solution to obtain the water-soluble adhesive for the lithium ion battery. The invention relates to a lithium ion battery electrode piece, a lithium ion battery and an adhesive, namely a lithium ion battery water-soluble adhesive. Compared with the prior art, the invention has better dispersion performance and slurry stability, is beneficial to improving the bonding strength, endows the bonding agent with certain high temperature resistance by lower swelling characteristic of electrolyte, and has simple preparation method and low cost.
Description
Technical Field
The invention relates to a lithium ion battery material and a preparation method thereof, an electrode plate and a battery, in particular to a lithium ion secondary battery binder and a preparation method thereof, and an electrode plate and a lithium ion battery adopting the binder.
Background
Currently, lithium ion batteries are considered to be the most promising mobile energy storage batteries in mobile electronic products, the electric automobile industry and other energy recycling systems. The common binders for the lithium ion battery are polyvinylidene fluoride (PVDF) and styrene-butadiene emulsion SBR binders. PVDF is used as a binder, and an organic solvent such as nitrogen methyl pyrrolidone NMP used to dissolve PVDF is harmful to the environment and human body, and is expensive. SBR is used as a binder, cellulose CMC is required to be added as a thickening agent, and the CMC has general viscosity, large brittleness, poor flexibility and easy cracking of an electrode plate during charging and discharging. Meanwhile, when SBR is used as a binder electrolyte and is applied to a graphite cathode and a silicon-based novel cathode based on a point-point binding mechanism, the volume of the graphite cathode and the silicon-based cathode repeatedly expands and contracts during charge and discharge cycles, so that the binder is easy to lose the binding property, and the capacity loss, especially the high-temperature storage and high-temperature cycle performance deterioration is caused.
Disclosure of Invention
The invention aims to provide a water-soluble adhesive for a lithium ion battery, a preparation method of the water-soluble adhesive, an electrode plate and a battery, and aims to solve the technical problems of improving the high-temperature storage and high-temperature cycle performance of the lithium ion battery and reducing the cost.
The invention adopts the following technical scheme: a water-soluble adhesive for a lithium ion battery is prepared from a monomer with a structural formula of formula 1, a monomer with a structural formula of formula 2 and a monomer with a structural formula of formula 3 by mass percent: 5-75% of monomer of formula 1, 1-35% of monomer of formula 2, 5-65% of monomer of formula 3 to form a multi-component copolymer,
the formula 1 is: CHR11＝CHR12-CN，
R11Is H, Cl, Br or-CH3，
R12Is H, Cl, Br, -CH3or-C6H4-；
The formula 2 is: CHR21＝CHR22-CONR23R24，
R21Is H or-CH3，
R22Is H or-C6H5，
R23Is H, -C6H7or-Cn-1CH3N is an integer of 1 to 19,
R24is H, -C (CH)3)2CH2-SO3M、-(CH2)mSO3P or- (CH)2)n-1CH3(ii) a M is Li, Na or K, P is Li or Na, and M is an integer of 0-14;
the formula 3 is: CHR31＝COOR32，
R31Is H or CH3，
R32Is H or M, and M is Li, Na or K.
The monomer of formula 1 of the present invention is: acrylic acid, methacrylonitrile, or acrylonitrile; the monomer of formula 2 is: n, N-diethylacrylamide, acrylamide or 2-acrylamido-2-phenylethanesulfonic acid; the monomer of formula 3 is: acrylonitrile, sodium acrylate, acrylic acid or methacrylic acid.
The monomer of formula 1, the monomer of formula 2 and the monomer of formula 3 are as follows by mass percent: 10-75% of monomer of formula 1, 1-35% of monomer of formula 2 and 10-55% of monomer of formula 3.
A preparation method of a water-soluble binder of a lithium ion battery comprises the following steps:
firstly, introducing nitrogen with the purity of more than or equal to 99.9% into a solvent under the stirring state at the rotating speed of 100-300 rpm, wherein the flow rate is 2000-4000L/H, and after 0.5-2H, the solvent is prepared by the following components in percentage by mass: 5-75% of a monomer of a formula 1, 1-35% of a monomer of a formula 2 and 5-65% of a monomer of a formula 3, adding the monomers into a solvent, continuously introducing nitrogen, stirring for 3-10 h, and uniformly mixing to obtain a solution, wherein the mass concentration of the solution is 10-30%;
the solvent is a water-soluble solvent: water, isopropanol or butanediol;
the formula 1 is: CHR11＝CHR12-CN，
R11Is H, Cl, Br or-CH3，
R12Is H, Cl, Br, -CH3or-C6H4-；
The formula 2 is: CHR21＝CHR22-CONR23R24，
R21Is H or-CH3，
R22Is H or-C6H5，
R23Is H, -C6H7or-Cn-1CH3N is an integer of 1 to 19,
R24is H, -C (CH)3)2CH2-SO3M、-(CH2)mSO3P or- (CH)2)n-1CH3(ii) a M is Li, Na or K, P is Li or Na, and M is an integer of 0-14;
the formula 3 is: CHR31＝COOR32，
R31Is H or CH3，
R32Is H or M, M is Li, Na or K;
secondly, keeping the nitrogen atmosphere, heating the solution to 30-85 ℃ at a heating rate of 1-2 ℃/min, adding 0.1-1% of initiator, keeping the temperature stable, and reacting for 5-10 hours to obtain a polymerization product;
the initiator is an organic peroxide initiator, an inorganic peroxide initiator or a redox initiator;
the organic peroxide initiator is benzoyl peroxide or dicumyl peroxide;
the inorganic peroxide initiator is ammonium persulfate, sodium persulfate or potassium persulfate;
the redox initiator is ammonium persulfate and sodium sulfite, or ammonium persulfate and sodium bisulfite;
neutralizing the polymerization product with an aqueous alkali solution at 50-80 ℃ until the pH is 7.5 to obtain the water-soluble adhesive for the lithium ion battery;
the alkaline water solution is one or two of lithium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and sodium bicarbonate.
After the second step, decompressing the polymerization product at 60-80 ℃ until the vacuum degree is lower than 0.1 MPa.
The mass concentration of the aqueous alkali solution in the third step is 5-20%.
The monomer of formula 1 of the present invention is: acrylic acid, methacrylonitrile, acrylonitrile; the monomer of formula 2 is: n, N-diethylacrylamide, acrylamide or 2-acrylamido-2-phenylethanesulfonic acid; the monomer of formula 3 is: acrylonitrile, sodium acrylate, acrylic acid or methacrylic acid.
The monomer of formula 1, the monomer of formula 2 and the monomer of formula 3 are as follows by mass percent: 10-75% of monomer of formula 1, 1-35% of monomer of formula 2 and 10-55% of monomer of formula 3.
The electrode plate of the lithium ion battery contains an adhesive, and the adhesive is the water-soluble adhesive for the lithium ion battery.
A lithium ion battery is provided with an electrode containing the lithium ion battery water-soluble adhesive of the present invention.
Compared with the prior art, the monomer of the formula 1 is 5-75%, the monomer of the formula 2 is 1-35%, the monomer of the formula 3 is 5-65%, the multipolymer is formed, the water-soluble polymer molecular chain characteristics endow a surface-surface bonding mechanism, the reticular bonding is formed, the bonding force between the active materials and the base material is enhanced, the dispersing performance and the slurry stability are better, the bonding strength is improved, the low electrolyte swelling characteristic endows the bonding agent with certain high temperature resistance, the preparation method is simple, the cost is low, and the industrial production is easy to realize.
Drawings
FIG. 1 is a graph of the rheology of the examples after 48 hours of standing.
FIG. 2 is a graph showing the comparison of the peel strengths of examples and comparative examples.
FIG. 3 is a 60 ℃ high temperature cycle chart of examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. The invention relates to a water-soluble adhesive (binder) for a lithium ion battery, which is prepared from a monomer with a structural formula of formula 1, a monomer with a structural formula of formula 2 and a monomer with a structural formula of formula 3 in percentage by mass: 5-75% of a monomer of formula 1, 1-35% of a monomer of formula 2, and 5-65% of a monomer of formula 3, wherein,
formula 1 is: CHR11＝CHR12-CN，
R11Is H, Cl, Br or-CH3，
R12Is H, Cl, Br, -CH3or-C6H4-。
The monomer of formula 1 contains a-CN functional group, and can impart high adhesion to the adhesive. When the mass ratio of formula 1 is less than 5%, the cohesive force is low, and when the mass ratio of formula 1 is more than 75%, the water solubility of the binder is affected.
The monomer of formula 1 is: acrylic acid, methacrylonitrile or acrylonitrile.
The formula 2 is: CHR21＝CHR22-CONR23R24，
R21Is H or-CH3，
R22Is H or-C6H5，
R23Is H, -C6H7or-Cn-1CH3(ii) a n is an integer of 1 to 19,
R24is H, -C (CH)3)2CH2-SO3M、-(CH2)mSO3P or- (CH)2)n-1CH3(ii) a M is Li, Na or K, P is Li or Na, and M is an integer of 0-14.
The monomer of formula 2 contains a-CO-N functional group, which can impart high adhesion and flexibility to the adhesive. When the mass ratio of the monomer of formula 2 is less than 1%, the flexibility of the binder is deteriorated, and when it is more than 35%, the water solubility of the binder is deteriorated.
The monomer of formula 2 is: n, N-diethylacrylamide, acrylamide or 2-acrylamido-2-phenylethanesulfonic acid.
Formula 3 is: CHR31＝COOR32，
R31Is H or CH3，
R32Is H or M, and M is Li, Na or K.
The monomer of formula 3 is a highly water soluble monomer containing a COOM or COOH functional group. When the mass ratio of formula 3 is less than 10%, the binder cannot be dissolved in water, and when it is more than 55%, the flexibility of the binder is deteriorated.
The monomer of formula 3 is: acrylonitrile, sodium acrylate, acrylic acid or methacrylic acid.
The monomers shown in the formula 1, the monomers shown in the formula 2 and the monomers shown in the formula 3 preferably comprise the following components in percentage by mass: 10-75% of monomer of formula 1, 1-35% of monomer of formula 2 and 10-55% of monomer of formula 3.
The preparation method of the water-soluble binder of the lithium ion battery adopts soap-free emulsion polymerization and comprises the following steps:
firstly, placing a solvent in a 2000L reaction kettle at room temperature (20 ℃), introducing nitrogen with the purity of more than or equal to 99.9 percent under the stirring state at the rotating speed of 100-300 rpm, introducing the nitrogen at the flow rate of 2000-4000L/H, replacing 0.5-2H, and removing water-soluble oxygen, wherein the water-soluble oxygen comprises the following components in percentage by mass: 5-75% of a monomer of formula 1, 1-35% of a monomer of formula 2 and 5-65% of a monomer of formula 3, adding the monomers into a solvent, continuously introducing nitrogen, stirring for 3-10 h, and uniformly mixing to obtain a solution, wherein the mass concentration of the solution is 10-30%.
The solvent is water-soluble solvent: water, isopropanol or butanediol.
The formula 1 is: CHR11＝CHR12-CN，
R11Is H, Cl, Br or-CH3，
R12Is H, Cl, Br, -CH3or-C6H4-；
The formula 2 is: CHR21＝CHR22-CONR23R24，
R21Is H or-CH3，
R22Is H or-C6H5，
R23Is H, -C6H7or-Cn-1CH3N is an integer of 1 to 19,
R24is H, -C (CH)3)2CH2-SO3M、-(CH2)mSO3P or- (CH)2)n-1CH3(ii) a M is Li, Na or K, P is Li or Na, and M is an integer of 0-14;
the formula 3 is: CHR31＝COOR32，
R31Is H or CH3，
R32Is H or M, and M is Li, Na or K.
Preferably, the method comprises the following steps:
the monomer of formula 1 is: acrylic acid, methacrylonitrile or acrylonitrile,
the monomer of formula 2 is: n, N-diethylacrylamide, acrylamide or 2-acrylamido-2-phenylethanesulfonic acid,
the monomer of formula 3 is: acrylonitrile, sodium acrylate, acrylic acid or methacrylic acid.
And secondly, keeping the nitrogen atmosphere, heating the solution to the temperature of 30-85 ℃ at the heating rate of 1-2 ℃/min, adding 0.1-1% of initiator, keeping the temperature stable, reacting for 5-10 hours, and carrying out copolymerization to obtain a polymerization product.
The initiator is an organic peroxide initiator, an inorganic peroxide initiator or a redox initiator.
The organic peroxide initiator is benzoyl peroxide or dicumyl peroxide.
The inorganic peroxide initiator is ammonium persulfate, sodium persulfate or potassium persulfate.
The redox initiator is ammonium persulfate and sodium sulfite or ammonium persulfate and sodium bisulfite in any proportion.
In the step, a high molecular weight polymerization product is obtained by controlling the initiator and the reaction temperature.
And thirdly, reducing the pressure of the polymerization product at 60-80 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
The step removes residual monomers and improves the performance of the battery.
And fourthly, neutralizing the polymerization product with an aqueous alkali solution at the temperature of 50-80 ℃ until the pH value is 7.5 to obtain a viscous water-soluble binder, namely the lithium ion battery water-soluble binder.
The alkaline water solution is one or two of lithium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and sodium bicarbonate, and the mass concentration of the alkaline water solution is 5-20%.
The aqueous solution with moderate pH is obtained by neutralization so as not to have negative influence on the performance of the battery.
When the intrinsic viscosity of the water-soluble multi-component copolymer is within a certain reasonable range, the water-soluble multi-component copolymer has good dispersion characteristics and good suspension stability, avoids slurry sedimentation and shows excellent cohesive force. According to the invention, by controlling the reasonable mass percentages of the three monomers, the water-soluble binder which is completely soluble in water, and has lower swelling degree of electrolyte and higher intrinsic viscosity can be prepared.
The lithium ion battery water-soluble adhesive prepared by the method of the invention and the adhesive of the comparative example adopt the light transmittance of the aqueous solution of the adhesive to express the water solubility.
Light transmittance test
Weighing 10g of adhesive glue solution, accurately measuring to 0.1g, adding water to a constant volume of 20mL volumetric flask, uniformly stirring to obtain a test solution, and keeping the temperature at 25 ℃. A10 mm cuvette cleaned by pure water is taken, a wavelength of 430nm is used for testing, the pure water for constant volume is used for carrying out light transmittance zero adjustment, and the light transmittance of the test solution is measured. The light transmittance of 85% or more is defined as good water solubility.
The water-soluble adhesive for the lithium ion battery can be used for manufacturing an electrode plate of the lithium ion battery together with an anode active material and a cathode active material, wherein the anode can be lithium iron phosphate, lithium cobaltate, lithium manganate, nickel cobalt aluminum and nickel cobalt manganese, and the cathode can be artificial graphite, natural graphite, active carbon and a silicon-based composite cathode material.
And (3) preparing the silicon-based and graphite composite negative electrode material electrode plate by adopting the lithium ion battery water-soluble adhesive obtained in the embodiment and the adhesive of the comparative example. The silicon-based and graphite composite negative electrode material is preferably SiOx/C or Si-C composite material containing Si and C and natural graphite or artificial graphite, and the gram volume of the silicon-based and graphite composite negative electrode material is 600 mAh/g.
The silicon-based and graphite composite negative electrode material and the binder of the comparative example are prepared by adding deionized water according to the mass fraction of 95.5 wt% and conductive carbon black of 2.0 wt% in the solid content of 2.5 w% of lithium ion battery water-soluble binder and the proportion of 45% of the total solid content of the binder, and then preparing negative electrode plate slurry. The slurry which is uniformly dispersed is screened by a 100-mesh screen according to the prior art, then coated on a copper foil with the thickness of 10 mu m which is used as a current collector, directly put into a furnace for drying for 5 minutes at the temperature of 120 ℃, naturally cooled to the room temperature in the furnace, and then the temperature is 10 multiplied by 104And (4) rolling the N/m load per unit length to obtain the electrode piece. As the negative electrode of the lithium ion battery.
The lithium nickel cobalt manganese oxide NCM523 is used as a positive electrode, and ethylene carbonate EC: ethyl methyl carbonate EMC: diethyl carbonate DEC in a mass ratio of 3:2:5 mixed solvent containing 1MLiPF6The electrolyte is used, and the PE/PP material in the prior art is used as a diaphragm to manufacture the P383450 lithium ion battery.
The lithium ion battery is subjected to charge-discharge circulation at 0.5C under the temperature of 25 ℃ and the voltage range of 2.5-4.2V, the initial coulombic efficiency of the charge-discharge circulation and the coulombic efficiency and the capacity retention rate after 50 times of circulation are tested by a constant current method, the ratio of the thickness increase value of the pole piece to the thickness of the pole piece before charge-discharge is recorded as the expansion rate of the pole piece after 50 weeks of charge-discharge circulation and in the lithium-embedded state of the pole piece, and the obtained result is shown in table 2.
High temperature cycle performance
The lithium ion battery is directly placed in an oven environment at 60 ℃, under the voltage range of 2.5-4.2V, charge and discharge cycles are carried out at 0.5C, the cycle capacity retention rate is measured, and the test result is shown in table 2.
Intrinsic viscosity test
The water-soluble adhesive for the lithium ion battery in the embodiment and the adhesive in the comparative example are put into a halogenated alkali metal salt aqueous solution with the mass percent of more than 0 and less than or equal to 20 percent according to the proportion of 0.5 to 3, the halogenated alkali metal salt is more than one of potassium chloride, sodium chloride, potassium bromide and sodium bromide, a full-automatic Ubbelohde viscometer is adopted, the testing temperature is 25.00 ℃, the intrinsic viscosity is tested according to the Ubbelohde viscometer, and the testing result is shown in Table 2.
Slurry Dispersion Studies
Slurry dispersion
In a dispersion machine, taking 2.0 parts of lithium ion battery water-soluble adhesive with solid mass, adding pure water to dilute until the mass fraction is 3%, adding 1.0 part of carbon nanotube conductive agent, dispersing for 2H at the rotating speed of 1000rpm, adding 97 parts of silicon-based composite negative electrode, dispersing for 2H at the rotating speed of 1000rpm, adding water to adjust the viscosity to be 4000-60000 mpa.s, and sieving with a 100-mesh sieve for later use.
The water-soluble adhesives of the lithium ion batteries of the examples and the adhesives of the comparative examples are dispersed according to the method to obtain slurry, and the results of the tests on the rheology, the dispersion performance and the slurry stability are shown in table 2 by adopting a rheometer to measure the rheology after the slurry is kept stand for 24 hours.
Measurement of peeling Strength
The electrode sheets of examples and comparative examples were cut into a 20cm × 2.5cm long strip, a steel sheet having a thickness of 1mm was adhered to the collector side with a double-sided tape, a transparent adhesive tape was adhered to the coated layer side, and the strip was peeled at a speed of 100mm/min in a 180 ° direction by a tensile tester, and the peel stress was measured, and the test results are shown in table 2.
Evaluation of Pole piece flexibility
A mandrel with the diameter phi of 1.5mm is placed on one side of the current collector of the rolled pole piece in the example and the comparative example, a bending experiment is carried out, the state of the pole piece is observed through an optical microscope, the pole piece is good and marked as O, the pole piece is fallen or cracked and marked as X, and the test result is shown in table 2.
Swelling degree test of electrolyte
The lithium ion battery water-soluble adhesive of the example and the adhesive of the comparative example were prepared by spreading 1.0g of a glue solution having a solid mass in a film forming mold (length × width × height ═ 5 × 4 × 1, unit cm), drying in a forced air oven at 70 ℃ for 24 hours to obtain a film, cutting a square film having a side length of 1cm, drying at 105 ℃ and a vacuum degree of 0.095MPa for 2 hours, weighing as M1, placing in a glass sealed bottle with a cover containing an electrolyte of ethylene carbonate EC, ethyl methyl carbonate EMC and diethyl carbonate DEC, having an EC: EMC: DEC volume ratio of 3:2:5, holding at 70 ℃ for 7 days, slightly sucking off the electrolyte on the surface of the film in a drying room, weighing as M2, and having an electrolyte Swelling degree Swelling:
Swelling＝(M2-M1)/M1×100％，
the weighed film was further placed in an oven at a temperature of 105 ℃ and a vacuum of less than 0.095MPa and baked for 2 hours, the weight was recorded as M3, and the electrolyte dissolution disorder was:
Dissol.＝(M1-M3)/M1×100％。
the water-soluble adhesive for the lithium ion battery is soaked for 7 days at 70 ℃, and the swelling degree of electrolyte is less than 10 percent; the intrinsic viscosity at 25.0 ℃ is 100-800 mL/g. The high-temperature-resistant electrode has the characteristics of good dispersing performance, good slurry stability, high adhesive force, small pole piece full-electricity rebound and rebound after circulation, and improved high-temperature cycle performance.
Example 1
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 100rpm, nitrogen is introduced, the flow rate is 2000L/H, water-soluble oxygen is removed for 1.5 hours, then 55 parts of acrylic acid monomer of formula 1, 5 parts of N, N-diethylacrylamide monomer of formula 2 and 40 parts of acrylonitrile monomer of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 3 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 55 ℃ at the heating rate of 1 ℃/min, adding 0.5 part of initiator solution benzoyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 60 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with a lithium hydroxide aqueous alkali solution at the temperature of 50 ℃ until the pH value is 7.5 to obtain a viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 1 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Example 2
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 300rpm, nitrogen is introduced, the flow rate is 4000L/H, water-soluble oxygen is removed for 2 hours, then 55 parts of acrylonitrile monomer shown as formula 1, 5 parts of N, N-diethylacrylamide monomer shown as formula 2 and 40 parts of sodium acrylate monomer shown as formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 10 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 55 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution dicumyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 80 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at the temperature of 80 ℃ until the pH value is 7.5 to obtain viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 2 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Example 3
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 200rpm, nitrogen is introduced, the flow rate is 3000L/H, water-soluble oxygen is removed for 1.6 hours, then 35 parts of monomer methacrylonitrile of formula 1, 10 parts of monomer acrylamide of formula 2 and 55 parts of monomer acrylic acid of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 5 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 55 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution dicumyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 60 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at the temperature of 60 ℃ until the pH value is 7.5 to obtain a viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 3 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
As shown in fig. 3, the lithium ion battery water-soluble adhesive obtained in example 3 has improved high-temperature performance, and the capacity retention rate is still 93.1% after 200 cycles.
Example 4
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 200rpm, nitrogen is introduced, the flow rate is 3000L/H, water-soluble oxygen is removed for 1.6 hours, then 65 parts of monomer methacrylonitrile of formula 1, 15 parts of monomer acrylamide of formula 2 and 20 parts of monomer acrylic acid of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 5 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 55 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution dicumyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 60 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at the temperature of 60 ℃ until the pH value is 7.5 to obtain a viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 4 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Example 5
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 200rpm, nitrogen is introduced, the flow rate is 3000L/H, water-soluble oxygen is removed for 1.6 hours, then 70 parts of monomer methacrylonitrile of formula 1, 20 parts of monomer acrylamide of formula 2 and 10 parts of monomer acrylic acid of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 5 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 55 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution dicumyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 60 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at the temperature of 60 ℃ until the pH value is 7.5 to obtain a viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 5 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Example 6
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 300rpm, nitrogen is introduced, the flow rate is 4000L/H, water-soluble oxygen is removed for 1.5 hours, then 50 parts of acrylonitrile monomer of formula 1, 20 parts of 2-acrylamide-2-phenyl ethanesulfonic acid monomer of formula 2 and 30 parts of methacrylic acid monomer of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 6 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 60 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution benzoyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 70 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at 70 ℃ until the pH value is 7.5 to obtain viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 6 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
As shown in fig. 2, the lithium ion battery water-soluble adhesive obtained in example 6 had high adhesive strength, and retained high adhesive strength with little decrease in adhesive strength after rolling.
As shown in fig. 3, the lithium ion battery water-soluble adhesive obtained in example 6 has improved high-temperature performance, and the capacity retention rate is still 93.6% after 200 cycles.
Example 7
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 300rpm, nitrogen is introduced, the flow rate is 4000L/H, water-soluble oxygen is removed for 1.5 hours, then 45 parts of acrylonitrile monomer of formula 1, 15 parts of 2-acrylamide-2-phenyl ethanesulfonic acid monomer of formula 2 and 40 parts of methacrylic acid monomer of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 6 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 60 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution benzoyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 70 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at 70 ℃ until the pH value is 7.5 to obtain viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 7 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Example 8
Firstly, 350 parts of pure water is added into a reaction kettle, stirring is carried out at 300rpm, nitrogen is introduced, the flow rate is 4000L/H, water-soluble oxygen is removed for 1.5 hours, then 45 parts of acrylonitrile monomer of formula 1, 5 parts of 2-acrylamide-2-phenyl ethanesulfonic acid monomer of formula 2 and 50 parts of methacrylic acid monomer of formula 3 are added, nitrogen is continuously introduced, and stirring is carried out for 6 hours, so as to obtain a solution.
And secondly, continuously introducing nitrogen, heating the solution to 60 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator solution benzoyl peroxide with the mass fraction (10%), and initiating the reaction for 10 hours to obtain a polymerization product.
And thirdly, decompressing the polymerization product at 70 ℃ by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing the residual monomers of the formulas 1, 2 and 3.
And fourthly, neutralizing the polymerization product with sodium hydroxide alkali aqueous solution at 70 ℃ until the pH value is 7.5 to obtain viscous water-soluble adhesive, namely the lithium ion battery water-soluble adhesive.
The lithium ion battery water-soluble adhesive obtained in example 8 was subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersibility and slurry stability performance test, a peel strength measurement, a pole piece flexibility evaluation, and an electrolyte swelling degree test, and the test results are shown in table 2.
As shown in fig. 1, after 48 hours of storage, the viscosity-shear rate curve of the slurry almost completely coincided with that of the slurry after 0 hours of standing, indicating that the slurry consistency was good.
Comparative example 1
Adding 350 parts of pure water into a reaction kettle, starting stirring, introducing nitrogen to remove water-soluble oxygen for 1.5 hours, then adding 10 parts of methacrylic acid, 10 parts of acrylamide and 80 parts of methacrylonitrile, heating to 55 ℃ in a nitrogen atmosphere, keeping constant temperature, adding 0.5 part of initiator solution with the mass fraction of 10% to initiate reaction, finishing the reaction after 10 hours, vacuumizing to remove residual monomers, and adjusting the pH to 7.5 by using sodium hydroxide solution to obtain light yellow water emulsion.
Comparative example 2
Adding 350 parts of pure water into a reaction kettle, starting stirring, introducing nitrogen to remove water-soluble oxygen for 1.5 hours, then adding 40 parts of methacrylic acid, 50 parts of acrylamide and 10 parts of methacrylonitrile, heating to 55 ℃ in a nitrogen atmosphere, keeping constant temperature, adding 0.5 part of initiator solution with the mass fraction of 10% to initiate reaction, finishing the reaction after 10 hours, vacuumizing to remove residual monomers, and adjusting the pH value to 7.5 by using sodium hydroxide solution to obtain a light yellow viscous solution.
Comparative example 3
Adding 350 parts of pure water into a reaction kettle, starting stirring, introducing nitrogen to remove water-soluble oxygen for 1.5 hours, then adding 60 parts of acrylamide and 40 parts of methacrylonitrile, heating to 60 ℃ under the nitrogen atmosphere, keeping the temperature constant, adding 0.5 part of initiator solution with the mass fraction of 10% to initiate reaction, finishing the reaction after 10 hours, vacuumizing to remove residual monomers, and adjusting the pH value to 7.5 by using sodium hydroxide solution to obtain a light yellow viscous solution.
Comparative example 4
Adopts sodium carboxymethylcellulose (CMC) and styrene-butadiene latex (SBR) which are special for batteries and sold in the market.
Comparative example 5 a commercially available polyacrylic acid PAA light yellow viscous emulsion was used. The lithium ion battery water-soluble adhesive obtained in the comparative examples 1-5 is subjected to a light transmittance test, a coulombic efficiency and capacity retention rate after 50 cycles, a high-temperature cycle performance test, an intrinsic viscosity test, a slurry dispersion performance and slurry stability performance test, a peel strength test, a pole piece flexibility evaluation and an electrolyte swelling degree test, and the test results are shown in table 2.
As can be seen from Table 2, compared with the electrodes using the binders of comparative examples 1 to 5, the electrodes using the binders of examples 1 to 8 of the present invention showed a considerably higher binding power, a higher capacity retention rate after 50 cycles of charge and discharge, and a lower expansion rate of the electrode sheet than those of comparative examples 1 to 5.
Compared with an SBR (styrene butadiene rubber) binder system, the surface-surface binding mechanism has lower swelling degree of electrolyte and proper intrinsic viscosity, can be used as a coating dispersant and a viscosity regulator at the same time, can keep flexibility at normal temperature, and keeps the binding action between active materials and between current collectors in the manufacturing process and the circulating process of an electrode plate.
The molecular chain characteristics of the water-soluble polymer of the water-soluble binder (the binder) for the lithium ion battery are endowed with a surface-surface binding mechanism, so that a reticular binding is formed, and the binding force among active materials and between the active materials and a base material is enhanced. The invention shows certain high molecular weight characteristics, has better dispersion performance and slurry stability, contributes to the improvement of bonding strength, and endows the bonding agent with certain high temperature resistance by the lower swelling characteristic of electrolyte.
TABLE 1 monomer and mass ratios of examples to comparative examples
Table 2 test results of examples and comparative examples
Claims (5)
1. A water-soluble adhesive for lithium ion batteries is characterized in that: the lithium ion battery water-soluble adhesive comprises the following components in percentage by mass: 45-50% of a monomer of formula 1, 5-20% of a monomer of formula 2 and 30-50% of a monomer of formula 3 to form a multi-component copolymer, wherein the monomer of formula 1 is acrylonitrile; the monomer of the formula 2 is 2-acrylamide-2-phenylethanesulfonic acid; the monomer of formula 3 is methacrylic acid.
2. A preparation method of a water-soluble binder of a lithium ion battery comprises the following steps:
firstly, introducing nitrogen with the purity of more than or equal to 99.9 percent into a solvent under the stirring state at the rotating speed of 300rpm, adding 45-50 parts of a monomer of a formula 1, 5-20 parts of a monomer of a formula 2 and 30-50 parts of a monomer of a formula 3 into the solvent after 1.5H, continuously introducing the nitrogen, stirring for 6 hours, and uniformly mixing to obtain a solution;
the solvent is 350 parts of pure water;
the monomer of formula 1 is acrylonitrile; the monomer of the formula 2 is 2-acrylamide-2-phenylethanesulfonic acid; the monomer of formula 3 is methacrylic acid;
secondly, keeping the nitrogen atmosphere, heating the solution to 60 ℃ at the heating rate of 2 ℃/min, adding 0.5 part of initiator, keeping the temperature stable, and reacting for 10 hours to obtain a polymerization product;
the initiator is benzoyl peroxide;
thirdly, decompressing the polymerization product at 70 ℃ until the vacuum degree is lower than 0.1 MPa;
fourthly, neutralizing the polymerization product with an aqueous alkali solution at 70 ℃ until the pH value is 7.5 to obtain the water-soluble adhesive of the lithium ion battery;
the alkaline water solution is sodium hydroxide water solution.
3. The method for preparing the water-soluble binder of the lithium ion battery according to claim 2, wherein the method comprises the following steps: the quality concentration of the aqueous solution of the tetrahydric alkali in the step is 5-20%.
4. The electrode plate of the lithium ion battery contains an adhesive and is characterized in that: the adhesive is the water-soluble adhesive for lithium ion batteries according to claim 1.
5. A lithium ion battery is provided with electrodes, and is characterized in that: the electrode contains the lithium ion battery water-soluble binder according to claim 1.
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| CN111500228B (en) * | 2020-01-21 | 2021-03-16 | 四川茵地乐科技有限公司 | Adhesive for battery, lithium ion battery negative electrode sheet and lithium ion battery |
| WO2021253674A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Binder composition for secondary battery |
| CN114341304B (en) * | 2020-06-17 | 2023-10-31 | 广东省皓智科技有限公司 | Binder composition for secondary battery |
| US20220006090A1 (en) * | 2020-07-02 | 2022-01-06 | Zenlabs Energy, Inc. | Lithium ion cells with silicon based active materials and negative electrodes with water-based binders having good adhesion and cohesion |
| CN112382794B (en) * | 2020-08-03 | 2021-10-15 | 万向一二三股份公司 | Preparation method of graphite cathode lithium ion battery |
| WO2022110050A1 (en) * | 2020-11-27 | 2022-06-02 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| WO2022110041A1 (en) * | 2020-11-27 | 2022-06-02 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| EP4207342A1 (en) * | 2020-11-27 | 2023-07-05 | Dongguan Amperex Technology Limited | Electrochemical apparatus and electronic apparatus |
| CN113498558B (en) * | 2020-12-31 | 2023-08-25 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN113388346A (en) * | 2021-06-03 | 2021-09-14 | 珠海冠宇电池股份有限公司 | Adhesive, electrode slurry with adhesive and lithium ion battery |
| CN114573746B (en) * | 2021-12-31 | 2023-08-18 | 瑞红锂电池材料(苏州)有限公司 | High-lithium-content high-molecular-weight lithium acrylate emulsion and preparation method and application thereof |
| CN114940720B (en) * | 2022-05-31 | 2024-03-12 | 深圳大学 | High-nickel positive electrode lithium ion battery binder, preparation method thereof and lithium ion battery positive electrode |
| KR102636775B1 (en) * | 2023-10-19 | 2024-02-15 | 주식회사 신아티앤씨 | Conductive material dispersion for secondary battery and slurry composition for secondary battery electrode containing the same |
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