WO2024002199A1 - Binder for negative electrode of lithium-ion battery, and preparation method therefor and use thereof - Google Patents

Binder for negative electrode of lithium-ion battery, and preparation method therefor and use thereof Download PDF

Info

Publication number
WO2024002199A1
WO2024002199A1 PCT/CN2023/103478 CN2023103478W WO2024002199A1 WO 2024002199 A1 WO2024002199 A1 WO 2024002199A1 CN 2023103478 W CN2023103478 W CN 2023103478W WO 2024002199 A1 WO2024002199 A1 WO 2024002199A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
copolymer
parts
core
concentration
Prior art date
Application number
PCT/CN2023/103478
Other languages
French (fr)
Chinese (zh)
Inventor
张晓辉
Original Assignee
上海道赢实业有限公司
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 上海道赢实业有限公司 filed Critical 上海道赢实业有限公司
Publication of WO2024002199A1 publication Critical patent/WO2024002199A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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

Definitions

  • the present invention relates to the field of polymer materials. Specifically, it relates to a binder for lithium ion battery negative electrodes, a method of preparing a binder for lithium ion battery negative electrodes, the binder prepared by the method, A negative electrode containing the binder and a lithium ion battery containing the negative electrode.
  • Lithium-ion batteries have the advantages of high voltage, large specific energy, stable discharge voltage, good cycle performance, excellent safety performance, and long storage and working life. They are one of the latest development directions in the chemical power supply industry.
  • the main negative electrode material of lithium-ion secondary batteries is powdery.
  • the graphite and conductive agent carbon black are non-polar and surface hydrophobic substances, which are prone to aggregation in water and difficult to disperse. Therefore, appropriate additives must be used for electrode preparation.
  • Thickeners generally include stabilizers (such as CMC) and binders (such as SBR). Among them, SBR combines with graphite and conductive agent carbon black through hydrophobic groups on the one hand, and condensation reaction occurs through hydrophilic groups and groups on the surface of the current collector on the other hand.
  • CMC has an auxiliary bonding effect on SBR. At the same time, the SBR can be dispersed more evenly, and the repulsion of space charges can be used to ensure the stability of the entire system.
  • the manufacturing method and application environment of secondary batteries are relatively complex. There are many inorganic and organic substances inside, and the external environment is affected by factors such as the use environment and human influence, and the working environment is poor. In particular, electrolyte is added during the manufacturing process of secondary batteries, causing the SBR to be immersed in the electrolyte for a long time inside the battery. It is also affected by the high and low temperatures of the secondary battery, cycle charge and discharge, high current charge and discharge and other working conditions. The adhesion and tolerance between SBR and current collector will deteriorate.
  • An object of the present invention is to provide a binder for a negative electrode of a lithium ion battery that has excellent electrolyte resistance.
  • the present invention provides a binder for lithium ion battery negative electrode, the binder includes a first copolymer and a second copolymer; the first copolymer and the second copolymer The weight ratio is 0.05-50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer region Including 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.01-20 parts by weight of bispropylene Amide monomer; the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble Sexually unsaturated carboxylic acid monomer and 0.
  • the invention also provides a method for preparing a binder for the negative electrode of a lithium ion battery.
  • the method includes: subjecting the comonomer in the first core copolymer region to a first emulsion polymerization to obtain a first core copolymer;
  • the first core copolymer and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain a first copolymer with a first core-shell structure;
  • the comonomer in the second core copolymer region is subjected to a third emulsion polymerization.
  • Three-emulsion polymerization is performed to obtain a second core copolymer; the second core copolymer and the comonomer in the second shell copolymer region are subjected to a fourth emulsion polymerization to obtain a second copolymer with a second core-shell structure;
  • the first copolymer and the second copolymer are mixed in a weight ratio of 0.05-50:1;
  • the comonomers in the first core copolymer region include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight Parts by weight of aliphatic conjugated diene, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers body and 0.01-20 parts by weight of bisacrylamide monomer;
  • the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds and 1-100 parts by weight of aliphatic conjugated Diolefin, 0.01-20 parts by weight of water-soluble unsatur
  • Vinyl aromatic compound 0.1-50 parts by weight of acrylate monomer and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer; the comonomer of the second shell copolymer zone includes 0.1-200 parts by weight monovinyl aromatic compound, 0.1-500 parts by weight of acrylate monomer, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
  • the present invention also provides an adhesive prepared by the above method.
  • the present invention also provides the use of the above-described binder in preparing lithium ion battery negative electrodes.
  • the present invention also provides a lithium ion battery negative electrode, which contains the above-mentioned binder.
  • the present invention also provides a lithium ion battery, which contains a positive electrode, an electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
  • the binder for the negative electrode of lithium ion batteries of the present invention can have excellent electrolyte tolerance after film formation, thereby effectively improving the performance of lithium ion batteries.
  • FIG. 1 is a photograph of the second adhesive film of Example 1
  • FIG. 2 is a photograph of the first adhesive film of Example 1.
  • FIG. 3 is a photograph of the second adhesive film of Comparative Example 1
  • FIG. 4 is a photograph of the first adhesive film of Comparative Example 1.
  • the invention provides a binder for lithium ion battery negative electrodes.
  • the binder includes a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 0.05. -50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer region includes 0.1-20 wt.
  • the comonomers of the first shell copolymer zone include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble unsaturated carboxylic acids.
  • the second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region;
  • the second core copolymer The comonomers of the zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers;
  • the second shell The comonomers in the copolymer zone include 0.1-200 parts by weight of monovinyl aromatic compounds, 0.1-500 parts by weight of acrylate monomers, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.1-20 parts by weight. parts by weight of bisacrylamide monomer.
  • the inventive concept of the present invention is that the first copolymer has a lower glass transition temperature, higher adhesive force, higher elastic modulus after film formation and electrolyte tolerance, and the second copolymer has The material has a lower glass transition temperature, higher bonding force, and higher tensile force at break.
  • the adhesive obtained by combining the two has good elastic modulus of the film, low internal resistance of the battery, The cycle capacity retention rate is high, and the high and low temperature performance and processing performance are relatively excellent.
  • the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, and more preferably 4.5-5.5:1.
  • the weight ratio of the first core copolymer region and the first shell copolymer region is 0.01-20:1, preferably 0.1-10:1, more preferably 0.3-5:1; in the second copolymer, The weight ratio of the second core copolymer region and the second shell copolymer region is 0.01-50:1, preferably 0.1-30:1, and more preferably 0.3-5:1.
  • the particle size of the polymer particles of the first copolymer is between 50-1000 nm, and the glass transition temperature of the first copolymer is -40°C to 90°C; the polymerization of the second copolymer The particle size of the material particles is between 50-1000 nm, the glass transition temperature of the second copolymer is -40°C to 90°C, and the solid content of the binder is 10-60% by weight.
  • each of the monovinyl aromatic compounds is independently at least one of styrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene;
  • the fat The conjugated dienes of the group are each independently 1,3-butadiene and/or isoprene;
  • the water-soluble unsaturated carboxylic acids are each independently methacrylic acid, acrylic acid, itaconic acid, fumaric acid and At least one of maleic acid;
  • the bisacrylamide monomers are each independently N,N-methylene bisacrylamide, N,N-(1,2-dihydroxyethylene) bisacrylamide and tartaric acid bisacrylamide.
  • the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate.
  • the monovinyl aromatic compound is styrene
  • the aliphatic conjugated diene is 1,3-butadiene
  • the first core copolymer region the first shell copolymer region and
  • the water-soluble unsaturated carboxylic acid in the second core copolymer region is itaconic acid
  • the water-soluble unsaturated carboxylic acid in the second shell copolymer region is acrylic acid and/or methacrylic acid
  • the bisacrylamide monomer is N,N-methylene bisacrylamide
  • the acrylate monomer is butyl acrylate.
  • the butyl acrylate may be n-butyl acrylate and/or isobutyl acrylate.
  • the invention also provides a method for preparing a binder for the negative electrode of a lithium ion battery.
  • the method includes: subjecting the comonomer in the first core copolymer region to a first emulsion polymerization to obtain a first core copolymer;
  • the first core copolymer and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain a first copolymer with a first core-shell structure;
  • the comonomer in the second core copolymer region is subjected to a third emulsion polymerization.
  • Three-emulsion polymerization is performed to obtain a second core copolymer; the second core copolymer and the second shell are copolymerized
  • the comonomer in the polymer region undergoes fourth emulsion polymerization to obtain a second copolymer with a second core-shell structure; the first copolymer and the second copolymer are mixed at a weight ratio of 0.05-50:1.
  • the comonomers of the first core copolymer zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble inorganic compounds.
  • the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of Aliphatic conjugated diene, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer;
  • the comonomer of the second core copolymer zone includes 0.1-20 parts by weight Parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers;
  • the comonomers of the second shell copolymer region include 0.1 -200 parts by weight of monovinyl aromatic compound, 0.1-500 parts by weight of acrylate monomer, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
  • the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1, and most preferably 4.89:1.
  • the conditions for the first emulsion polymerization include: the total concentration of comonomers in the first core copolymer zone is 1-30% by weight, the emulsifier concentration is 0.01-10% by weight, and the molecular weight is adjusted.
  • the concentration of the agent is 0.001-5% by weight, the concentration of the initiator is 0.001-20% by weight, the concentration of the chelating agent is 0.01-10% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
  • the conditions for the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization is 0.1-90% by weight, and the total concentration of comonomers in the first shell copolymer zone is The concentration of the emulsifier is 0.01-10% by weight, the concentration of the molecular weight regulator is 0.001-5% by weight, the concentration of the initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization time is 1-1000 minutes. The temperature is 30-90°C.
  • the conditions for the third emulsion polymerization include: the total concentration of comonomers in the second core copolymer zone is 0.1-90% by weight, and the emulsifier concentration is 0.001-20% by weight.
  • the concentration of the sub-weight regulator is 0.001-20% by weight, the concentration of the initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
  • the conditions for the fourth emulsion polymerization include: the amount of material obtained after the third emulsion polymerization is 1-85% by weight, and the total concentration of comonomers in the first shell copolymer zone is The concentration of emulsifier is 0.001-20% by weight, the concentration of molecular weight regulator is 0.001-20% by weight, the concentration of initiator is 0.001-20% by weight, and the concentration of chelating agent is 0.01-10% by weight. , the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
  • the emulsifiers are each independently selected from the group consisting of sodium dihexyl sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol ether sulfate, dodecylphenol polyoxyethylene ether, At least one of octylphenol polyoxyethylene ether, sodium secondary alkyl sulfonate, alkyl diphenyl ether disulfonate and aliphatic carboxylate; the molecular weight regulator is each independently selected from n-dodecyl sulfide At least one of alcohol, tert-dodecyl mercaptan, diisopropyl xanthate disulfide and ⁇ -methylstyrene linear dimer.
  • the present invention also provides an adhesive prepared by the above method.
  • the present invention also provides the use of the above-described binder in preparing lithium ion battery negative electrodes.
  • the present invention also provides a lithium ion battery negative electrode, which contains the above-mentioned binder.
  • the present invention also provides a lithium ion battery, which contains a positive electrode, an electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
  • the present invention will be further described in detail below through examples.
  • the raw materials used in the examples can be obtained through commercial channels.
  • the comonomer in the first core copolymer zone is subjected to first emulsion polymerization to obtain the first core copolymer.
  • the comonomers of the first core copolymer zone include 2.8 parts by weight of styrene, 4.03 parts by weight of butadiene, 0.28 parts by weight of itaconic acid and 0.88 parts by weight of N,N-methylene bisacrylamide .
  • the conditions for the first emulsion polymerization include: the total amount of comonomers in the first core copolymer zone The concentration is 9.24% by weight, the emulsifier (a 1:2.114 mixture of sodium dihexyl succinate sulfonate and sodium dodecyl benzene sulfonate) concentration is 2.1% by weight, and the molecular weight regulator (tert-dodecyl mercaptan) The concentration of initiator (ammonium persulfate) is 5.4% by weight, the concentration of chelating agent (EDTA) is 0.054% by weight, the balance is made up with water, the polymerization time is 10 minutes, and the polymerization temperature is 68 °C.
  • the first core copolymer (used as a material obtained after the first emulsion polymerization) and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain the first core-shell structure. copolymer.
  • the comonomers of the first shell copolymer zone include 37.2 parts by weight of styrene, 53.53 parts by weight of butadiene, 1.12 parts by weight of itaconic acid and 0.22 parts by weight of N,N-methylene bisacrylamide .
  • the conditions for the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization is 77.40% by weight, the amount of comonomer in the first shell copolymer zone is 10.58% by weight, and the emulsifier (D The concentration of sodium dihexyl sulfonate and sodium dodecyl benzene sulfonate (1:1.158 mixture) is 0.186% by weight, the concentration of the molecular weight regulator (tert-dodecanethiol) is 0.239% by weight, and the initiator ( The concentration of ammonium persulfate (ammonium persulfate) was 3.98% by weight, and the balance was made up with water.
  • the polymerization time was 630 minutes, and the polymerization temperature was 68°C. After the polymerization is completed, a second copolymer is obtained.
  • the comonomer in the second core copolymer region is subjected to third emulsion polymerization to obtain a second core copolymer.
  • the comonomers of the second core copolymer zone include 8.575 parts by weight of styrene, 25.725 parts by weight of butyl acrylate, and 3 parts by weight of itaconic acid;
  • the conditions for the third emulsion polymerization include: the total concentration of comonomers in the second core copolymer zone is 6.63% by weight, the concentration of the emulsifier (dodecylphenol polyoxyethylene ether) is 0.58% by weight, and the molecular weight
  • the concentration of the regulator (n-dodecanethiol) was 0.066% by weight, the concentration of the initiator (ammonium persulfate) was 3.86% by weight, and the balance was made up with water.
  • the polymerization time was 15 minutes, and the polymerization temperature was 69°C.
  • the second core copolymer (used as a material obtained after the third emulsion polymerization)
  • the fourth emulsion polymerization is performed with the comonomer of the second shell copolymer region to obtain a second copolymer having a second core-shell structure.
  • the comonomers of the second shell copolymer zone include 111 parts by weight of styrene, 9.5 parts by weight of butyl acrylate, 333 parts by weight of acrylic acid, and 11.1 parts by weight of N,N-methylene bisacrylamide.
  • the conditions for the fourth emulsion polymerization include: the amount of material obtained after the third emulsion polymerization is 56.93% by weight, the amount of comonomer in the first shell copolymer zone is 7.49% by weight, and the emulsifier (fat Alcohol ether sulfate) concentration is 0.29% by weight, the concentration of the molecular weight regulator (n-dodecanethiol) is 0.086% by weight, the concentration of the initiator (ammonium persulfate) is 4.5% by weight, and the concentration of the chelating agent (EDTA) is 4.5% by weight, the balance was made up with water, the polymerization time was 510 minutes, and the polymerization temperature was 69°C. After the polymerization is completed, a second copolymer is obtained.
  • the first copolymer and the second copolymer are mixed at a weight ratio of 4.89:1, and the solid content is adjusted to 40% by weight to obtain the adhesive of this embodiment.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 8:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 2:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 15:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 0.5:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the itaconic acid in the first copolymer was replaced with acrylic acid.
  • the binder was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced with fumaric acid.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced with maleic acid.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that butyl acrylate in the second copolymer was replaced with ethyl acrylate.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the acrylic acid in the second copolymer was replaced by itaconic acid.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 60:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 0.04:1.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced by acrylamide.
  • the adhesive was prepared in the same manner as in Example 1; the difference was that butyl acrylate in the second copolymer was replaced with acrylamide.
  • FIG. 1 is a photograph of the second adhesive film of Example 1
  • FIG. 2 is a photograph of the first adhesive film of Example 1.
  • FIG. 3 is a photograph of the second adhesive film of Comparative Example 1
  • FIG. 4 is a photograph of the first adhesive film of Comparative Example 1. It can be clearly seen that the color of the rubber film of Comparative Example 1 turned brown after being soaked in electrolyte, while the color of the rubber film of Example 1 did not change significantly after being soaked in electrolyte. This shows that the adhesive film of Example 1 has excellent electrolyte immersion resistance.
  • the present invention is added to the negative electrode slurry in an amount of 1.4% by weight and 1.7% by weight, and then pulped, coated, dried, and rolled to obtain a pole piece.
  • the pole piece is punched into 20mm wide strips and tested in a universal tensile test.
  • the 90-degree peeling method is used for testing on the machine. The results are shown in Table 4.
  • batteries were prepared using the binders of Examples 1-10 and Comparative Examples 1-4, and battery cycle performance tests were conducted.
  • the battery was evaluated using soft-pack laminates 5AH.
  • the positive electrode used capacity-type LFP and the negative electrode used FSN-like artificial graphite.
  • the CMC addition amount was 1.2%.
  • the battery design was conducted with reference to the energy battery design method for 110 weeks of normal temperature 1C and 55°C 1C tests. The results are shown in Table 5.
  • the binder for lithium-ion battery negative electrodes of the present invention can have excellent electrolyte tolerance after film formation, thereby effectively improving the performance of lithium-ion batteries, and is particularly preferred.
  • the weight ratio of the first copolymer to the second copolymer is 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1, the binder has more good performance.
  • any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to the field of high polymer materials, and specifically to a binder for a negative electrode of a lithium-ion battery, a method for preparing the binder used for a negative electrode of a lithium-ion battery, the binder prepared by the method, a negative electrode containing the binder, and a lithium-ion battery containing the negative electrode. By means of the above technical solutions, the binder for a negative electrode of a lithium-ion battery of the present invention has an excellent electrolyte tolerance after film formation, such that the performance of the lithium-ion battery can be effectively improved.

Description

一种用于锂离子电池负极的粘结剂及其制备方法和用途A kind of binder for lithium ion battery negative electrode and its preparation method and use 技术领域Technical field
本发明涉及高分子材料领域，具体地，涉及一种用于锂离子电池负极的粘结剂、一种制备用于锂离子电池负极的粘结剂的方法、该方法制备得到的粘结剂、含有该粘结剂的负极和含有该负极的锂离子电池。The present invention relates to the field of polymer materials. Specifically, it relates to a binder for lithium ion battery negative electrodes, a method of preparing a binder for lithium ion battery negative electrodes, the binder prepared by the method, A negative electrode containing the binder and a lithium ion battery containing the negative electrode.
背景技术Background technique
锂离子电池具有电压高、比能量大、放电电压平稳、循环性能好、安全性能优以及贮存和工作寿命长等优点，是目前化学电源行业的最新发展方向之一。Lithium-ion batteries have the advantages of high voltage, large specific energy, stable discharge voltage, good cycle performance, excellent safety performance, and long storage and working life. They are one of the latest development directions in the chemical power supply industry.
锂离子二次电池负极主材料为粉状物，其中的石墨及导电剂炭黑均为非极性、表面疏水性物质，其在水中容易发生聚集而难以分散。因此必须使用合适的添加剂来进行电极的制备，增稠剂一般包括稳定剂(如CMC)和粘结剂(如SBR)。其中，SBR一方面通过疏水性基团与石墨及导电剂炭黑结合，另一方面通过亲水性基团和集流体表面的基团发生缩合反应，而CMC对SBR具有辅助的粘结作用，同时也可让SBR分散的更加均匀，同时利用空间电荷的排斥作用，保证整个体系的稳定。The main negative electrode material of lithium-ion secondary batteries is powdery. The graphite and conductive agent carbon black are non-polar and surface hydrophobic substances, which are prone to aggregation in water and difficult to disperse. Therefore, appropriate additives must be used for electrode preparation. Thickeners generally include stabilizers (such as CMC) and binders (such as SBR). Among them, SBR combines with graphite and conductive agent carbon black through hydrophobic groups on the one hand, and condensation reaction occurs through hydrophilic groups and groups on the surface of the current collector on the other hand. CMC has an auxiliary bonding effect on SBR. At the same time, the SBR can be dispersed more evenly, and the repulsion of space charges can be used to ensure the stability of the entire system.
二次电池的制造方法和应用环境均较为复杂，其内部存在较多无机物和有机物，外部受使用环境、人为影响等因素，工况环境较差。尤其是二次电池在制造过程中会添加电解液，使SBR在电池内部长期处于浸泡于电解液内的状态，且受二次电池高低温、循环充放电、大电流充放电等工况影响，SBR与集流体的粘合度及耐受度会变差。The manufacturing method and application environment of secondary batteries are relatively complex. There are many inorganic and organic substances inside, and the external environment is affected by factors such as the use environment and human influence, and the working environment is poor. In particular, electrolyte is added during the manufacturing process of secondary batteries, causing the SBR to be immersed in the electrolyte for a long time inside the battery. It is also affected by the high and low temperatures of the secondary battery, cycle charge and discharge, high current charge and discharge and other working conditions. The adhesion and tolerance between SBR and current collector will deteriorate.
因此，现有的SBR存在电解液耐受性难以优异的缺陷。Therefore, existing SBR has the disadvantage that it is difficult to have excellent electrolyte resistance.
发明内容 Contents of the invention
本发明的目的在于提供一种电解液耐受性非常优异的用于锂离子电池负极的粘结剂。An object of the present invention is to provide a binder for a negative electrode of a lithium ion battery that has excellent electrolyte resistance.
为了实现上述目的，本发明提供了一种用于锂离子电池负极的粘结剂，该粘结剂包括第一共聚物和第二共聚物；所述第一共聚物与所述第二共聚物的重量比为0.05-50:1；所述第一共聚物具有第一核壳结构并含有第一核共聚物区和第一壳共聚物区；所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第二共聚物具有第二核壳结构并含有第二核共聚物区和第二壳共聚物区；所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。In order to achieve the above object, the present invention provides a binder for lithium ion battery negative electrode, the binder includes a first copolymer and a second copolymer; the first copolymer and the second copolymer The weight ratio is 0.05-50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer region Including 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.01-20 parts by weight of bispropylene Amide monomer; the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble Sexually unsaturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer; the second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; The comonomers of the second core copolymer zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers, and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers; The comonomers of the second shell copolymer zone include 0.1-200 parts by weight of monovinyl aromatic compounds, 0.1-500 parts by weight of acrylate monomers, and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers. body and 0.1-20 parts by weight of bisacrylamide monomer.
本发明还提供了一种制备用于锂离子电池负极的粘结剂的方法，该方法包括：将第一核共聚物区的共聚单体进行第一乳液聚合，得到第一核共聚物；将所述第一核共聚物与第一壳共聚物区的共聚单体进行第二乳液聚合，得到具有第一核壳结构的第一共聚物；将第二核共聚物区的共聚单体进行第三乳液聚合，得到第二核共聚物；将所述第二核共聚物与第二壳共聚物区的共聚单体进行第四乳液聚合，得到具有第二核壳结构的第二共聚物；将第一共聚物与第二共聚物按0.05-50:1的重量比进行混合；所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单 体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。The invention also provides a method for preparing a binder for the negative electrode of a lithium ion battery. The method includes: subjecting the comonomer in the first core copolymer region to a first emulsion polymerization to obtain a first core copolymer; The first core copolymer and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain a first copolymer with a first core-shell structure; the comonomer in the second core copolymer region is subjected to a third emulsion polymerization. Three-emulsion polymerization is performed to obtain a second core copolymer; the second core copolymer and the comonomer in the second shell copolymer region are subjected to a fourth emulsion polymerization to obtain a second copolymer with a second core-shell structure; The first copolymer and the second copolymer are mixed in a weight ratio of 0.05-50:1; the comonomers in the first core copolymer region include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight Parts by weight of aliphatic conjugated diene, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers body and 0.01-20 parts by weight of bisacrylamide monomer; the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds and 1-100 parts by weight of aliphatic conjugated Diolefin, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer; the comonomer of the second core copolymer zone includes 0.1-20 parts by weight of monomer. Vinyl aromatic compound, 0.1-50 parts by weight of acrylate monomer and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer; the comonomer of the second shell copolymer zone includes 0.1-200 parts by weight monovinyl aromatic compound, 0.1-500 parts by weight of acrylate monomer, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
本发明还提供了如上所述的方法制备得到的粘结剂。The present invention also provides an adhesive prepared by the above method.
本发明还提供了如上所述的粘结剂在制备锂离子电池负极中的用途。The present invention also provides the use of the above-described binder in preparing lithium ion battery negative electrodes.
本发明还提供了一种锂离子电池负极，所述锂离子电池负极含有如上所述的粘结剂。The present invention also provides a lithium ion battery negative electrode, which contains the above-mentioned binder.
本发明还提供了一种锂离子电池，所述锂离子电池含有正极、电解液和负极；所述负极为如上所述的负极。The present invention also provides a lithium ion battery, which contains a positive electrode, an electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
通过上述技术方案，本发明的用于锂离子电池负极的粘结剂能够在成膜后具有优异的电解液耐受性，从而可以有效地提高锂离子电池的性能。Through the above technical solutions, the binder for the negative electrode of lithium ion batteries of the present invention can have excellent electrolyte tolerance after film formation, thereby effectively improving the performance of lithium ion batteries.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the detailed description that follows.
附图说明Description of drawings
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the following specific embodiments, but do not constitute a limitation of the present invention. In the attached picture:
图1是实施例1的第二胶膜的照片，图2是实施例1的第一胶膜的照片。图3是对比例1的第二胶膜的照片，图4是对比例1的第一胶膜的照片。 FIG. 1 is a photograph of the second adhesive film of Example 1, and FIG. 2 is a photograph of the first adhesive film of Example 1. FIG. 3 is a photograph of the second adhesive film of Comparative Example 1, and FIG. 4 is a photograph of the first adhesive film of Comparative Example 1.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
本发明提供了一种用于锂离子电池负极的粘结剂，该粘结剂包括第一共聚物和第二共聚物；所述第一共聚物与所述第二共聚物的重量比为0.05-50:1；所述第一共聚物具有第一核壳结构并含有第一核共聚物区和第一壳共聚物区；所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第二共聚物具有第二核壳结构并含有第二核共聚物区和第二壳共聚物区；所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。The invention provides a binder for lithium ion battery negative electrodes. The binder includes a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 0.05. -50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer region includes 0.1-20 wt. parts of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.01-20 parts by weight of bisacrylamide monomers; The comonomers of the first shell copolymer zone include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble unsaturated carboxylic acids. monomer and 0.01-20 parts by weight of bisacrylamide monomer; the second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; the second core copolymer The comonomers of the zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers; the second shell The comonomers in the copolymer zone include 0.1-200 parts by weight of monovinyl aromatic compounds, 0.1-500 parts by weight of acrylate monomers, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.1-20 parts by weight. parts by weight of bisacrylamide monomer.
本发明的发明构思在于：所述第一共聚物具有较低的玻璃化转变温度、较高的粘结力、较高的成膜后弹性模量及电解液耐受性，所述第二共聚物具有较低的玻璃化转变温度、较高的的粘结力、较高的的断裂拉伸力，二者复合后得到的粘结剂具备良好的胶膜弹性模量、电池内阻低、循环容量保持率高，高低温性能、加工性能均较为优良。The inventive concept of the present invention is that the first copolymer has a lower glass transition temperature, higher adhesive force, higher elastic modulus after film formation and electrolyte tolerance, and the second copolymer has The material has a lower glass transition temperature, higher bonding force, and higher tensile force at break. The adhesive obtained by combining the two has good elastic modulus of the film, low internal resistance of the battery, The cycle capacity retention rate is high, and the high and low temperature performance and processing performance are relatively excellent.
其中，为了使得所述粘结剂具有更好的性能，优选所述第一共聚物与所述第二共聚物的重量比为0.5-15:1，优选为2-8:1，更优选为4.5-5.5:1。 Among them, in order to make the binder have better performance, the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, and more preferably 4.5-5.5:1.
所述第一核共聚物区和第一壳共聚物区的重量比为0.01-20:1，优选为0.1-10:1，更优选为0.3-5:1；所述第二共聚物中，所述第二核共聚物区和第二壳共聚物区的重量比为0.01-50:1，优选为0.1-30:1，更优选为0.3-5:1。The weight ratio of the first core copolymer region and the first shell copolymer region is 0.01-20:1, preferably 0.1-10:1, more preferably 0.3-5:1; in the second copolymer, The weight ratio of the second core copolymer region and the second shell copolymer region is 0.01-50:1, preferably 0.1-30:1, and more preferably 0.3-5:1.
可选地，所述第一共聚物的聚合物粒子的粒径在50-1000nm之间，所述第一共聚物的玻璃化温度为-40℃至90℃；所述第二共聚物的聚合物粒子的粒径在50-1000nm之间，所述第二共聚物的玻璃化温度为-40℃至90℃；所述粘结剂的固含量为10-60重量％。Optionally, the particle size of the polymer particles of the first copolymer is between 50-1000 nm, and the glass transition temperature of the first copolymer is -40°C to 90°C; the polymerization of the second copolymer The particle size of the material particles is between 50-1000 nm, the glass transition temperature of the second copolymer is -40°C to 90°C, and the solid content of the binder is 10-60% by weight.
可选地，其中，所述单乙烯基芳香族化合物各自独立地为苯乙烯、邻位甲基苯乙烯、间位甲基苯乙烯和对位甲基苯乙烯中的至少一种；所述脂肪族共轭二烯烃各自独立地为1,3-丁二烯和/或异戊二烯；所述水溶性不饱和羧酸各自独立地为甲基丙烯酸、丙烯酸、衣康酸、富马酸和马来酸中的至少一种；所述双丙烯酰胺单体各自独立地为N,N-亚甲基双丙烯酰胺、N,N-(1,2-二羟基乙烯)双丙烯酰胺和酒石酸双丙烯酰胺中的至少一种；所述丙烯酸酯单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯和丙烯酸戊酯中的至少一种。Optionally, wherein each of the monovinyl aromatic compounds is independently at least one of styrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene; the fat The conjugated dienes of the group are each independently 1,3-butadiene and/or isoprene; the water-soluble unsaturated carboxylic acids are each independently methacrylic acid, acrylic acid, itaconic acid, fumaric acid and At least one of maleic acid; the bisacrylamide monomers are each independently N,N-methylene bisacrylamide, N,N-(1,2-dihydroxyethylene) bisacrylamide and tartaric acid bisacrylamide. At least one of acrylamide; the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate.
优选地，所述单乙烯基芳香族化合物为苯乙烯，所述脂肪族共轭二烯烃为1,3-丁二烯，所述第一核共聚物区、所述第一壳共聚物区和所述第二核共聚物区中的所述水溶性不饱和羧酸为衣康酸，所述第二壳共聚物区中的所述水溶性不饱和羧酸为丙烯酸和/或甲基丙烯酸，所述双丙烯酰胺单体为N,N-亚甲基双丙烯酰胺，所述丙烯酸酯单体为丙烯酸丁酯。所述丙烯酸丁酯可以为丙烯酸正丁酯和/或丙烯酸异丁酯。Preferably, the monovinyl aromatic compound is styrene, the aliphatic conjugated diene is 1,3-butadiene, the first core copolymer region, the first shell copolymer region and The water-soluble unsaturated carboxylic acid in the second core copolymer region is itaconic acid, and the water-soluble unsaturated carboxylic acid in the second shell copolymer region is acrylic acid and/or methacrylic acid, The bisacrylamide monomer is N,N-methylene bisacrylamide, and the acrylate monomer is butyl acrylate. The butyl acrylate may be n-butyl acrylate and/or isobutyl acrylate.
本发明还提供了一种制备用于锂离子电池负极的粘结剂的方法，该方法包括：将第一核共聚物区的共聚单体进行第一乳液聚合，得到第一核共聚物；将所述第一核共聚物与第一壳共聚物区的共聚单体进行第二乳液聚合，得到具有第一核壳结构的第一共聚物；将第二核共聚物区的共聚单体进行第三乳液聚合，得到第二核共聚物；将所述第二核共聚物与第二壳共 聚物区的共聚单体进行第四乳液聚合，得到具有第二核壳结构的第二共聚物；将第一共聚物与第二共聚物按0.05-50:1的重量比进行混合。The invention also provides a method for preparing a binder for the negative electrode of a lithium ion battery. The method includes: subjecting the comonomer in the first core copolymer region to a first emulsion polymerization to obtain a first core copolymer; The first core copolymer and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain a first copolymer with a first core-shell structure; the comonomer in the second core copolymer region is subjected to a third emulsion polymerization. Three-emulsion polymerization is performed to obtain a second core copolymer; the second core copolymer and the second shell are copolymerized The comonomer in the polymer region undergoes fourth emulsion polymerization to obtain a second copolymer with a second core-shell structure; the first copolymer and the second copolymer are mixed at a weight ratio of 0.05-50:1.
其中，所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。Wherein, the comonomers of the first core copolymer zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble inorganic compounds. Saturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer; the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of Aliphatic conjugated diene, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer; the comonomer of the second core copolymer zone includes 0.1-20 parts by weight Parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers; the comonomers of the second shell copolymer region include 0.1 -200 parts by weight of monovinyl aromatic compound, 0.1-500 parts by weight of acrylate monomer, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
可选地，其中，优选所述第一共聚物与所述第二共聚物的重量比为0.5-15:1，优选为2-8:1，更优选为4.5-5.5:1，最优选为4.89:1。Optionally, the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1, and most preferably 4.89:1.
可选地，其中，所述第一乳液聚合的条件包括：所述第一核共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.01-10重量％，分子量调节剂的浓度为0.001-5重量％，引发剂的浓度为0.001-20重量％，螯合剂的浓度为0.01-10重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃。Optionally, the conditions for the first emulsion polymerization include: the total concentration of comonomers in the first core copolymer zone is 1-30% by weight, the emulsifier concentration is 0.01-10% by weight, and the molecular weight is adjusted. The concentration of the agent is 0.001-5% by weight, the concentration of the initiator is 0.001-20% by weight, the concentration of the chelating agent is 0.01-10% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
可选地，其中，所述第二乳液聚合的条件包括：所述第一乳液聚合后所得的物料的用量为0.1-90重量％，所述第一壳共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.01-10重量％，分子量调节剂的浓度为0.001-5重量％，引发剂的浓度为0.001-20重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃。Optionally, the conditions for the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization is 0.1-90% by weight, and the total concentration of comonomers in the first shell copolymer zone is The concentration of the emulsifier is 0.01-10% by weight, the concentration of the molecular weight regulator is 0.001-5% by weight, the concentration of the initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization time is 1-1000 minutes. The temperature is 30-90℃.
可选地，其中，所述第三乳液聚合的条件包括：所述第二核共聚物区的共聚单体的总浓度为0.1-90重量％，乳化剂浓度为0.001-20重量％，分 子量调节剂的浓度为0.001-20重量％，引发剂的浓度为0.001-20重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃。Optionally, the conditions for the third emulsion polymerization include: the total concentration of comonomers in the second core copolymer zone is 0.1-90% by weight, and the emulsifier concentration is 0.001-20% by weight. The concentration of the sub-weight regulator is 0.001-20% by weight, the concentration of the initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
可选地，其中，所述第四乳液聚合的条件包括：所述第三乳液聚合后所得的物料的用量为1-85重量％，所述第一壳共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.001-20重量％，分子量调节剂的浓度为0.001-20重量％，引发剂的浓度为0.001-20重量％，螯合剂的浓度为0.01-10重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃。Optionally, the conditions for the fourth emulsion polymerization include: the amount of material obtained after the third emulsion polymerization is 1-85% by weight, and the total concentration of comonomers in the first shell copolymer zone is The concentration of emulsifier is 0.001-20% by weight, the concentration of molecular weight regulator is 0.001-20% by weight, the concentration of initiator is 0.001-20% by weight, and the concentration of chelating agent is 0.01-10% by weight. , the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C.
可选地，其中，所述乳化剂各自独立地选自丁二酸二己酯磺酸钠、十二烷基苯磺酸钠、脂肪醇醚硫酸盐、十二烷基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、仲烷基磺酸钠、烷基二苯醚二磺酸盐和脂肪族羧酸盐中的至少一种；所述分子量调节剂各自独立地选自正十二硫醇、叔十二硫醇、二硫化二异丙基黄原酸酯和α-甲基苯乙烯线性二聚体中的至少一种。Optionally, the emulsifiers are each independently selected from the group consisting of sodium dihexyl sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol ether sulfate, dodecylphenol polyoxyethylene ether, At least one of octylphenol polyoxyethylene ether, sodium secondary alkyl sulfonate, alkyl diphenyl ether disulfonate and aliphatic carboxylate; the molecular weight regulator is each independently selected from n-dodecyl sulfide At least one of alcohol, tert-dodecyl mercaptan, diisopropyl xanthate disulfide and α-methylstyrene linear dimer.
本发明还提供了如上所述的方法制备得到的粘结剂。The present invention also provides an adhesive prepared by the above method.
本发明还提供了如上所述的粘结剂在制备锂离子电池负极中的用途。The present invention also provides the use of the above-described binder in preparing lithium ion battery negative electrodes.
本发明还提供了一种锂离子电池负极，所述锂离子电池负极含有如上所述的粘结剂。The present invention also provides a lithium ion battery negative electrode, which contains the above-mentioned binder.
本发明还提供了一种锂离子电池，所述锂离子电池含有正极、电解液和负极；所述负极为如上所述的负极。The present invention also provides a lithium ion battery, which contains a positive electrode, an electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
以下通过实施例进一步详细说明本发明。实施例中所用到的原材料均可通过商购途径获得。The present invention will be further described in detail below through examples. The raw materials used in the examples can be obtained through commercial channels.
实施例1Example 1
将第一核共聚物区的共聚单体进行第一乳液聚合，得到第一核共聚物。其中，第一核共聚物区的共聚单体包括2.8重量份的苯乙烯、4.03重量份的丁二烯、0.28重量份的衣康酸和0.88重量份的N,N-亚甲基双丙烯酰胺。The comonomer in the first core copolymer zone is subjected to first emulsion polymerization to obtain the first core copolymer. Among them, the comonomers of the first core copolymer zone include 2.8 parts by weight of styrene, 4.03 parts by weight of butadiene, 0.28 parts by weight of itaconic acid and 0.88 parts by weight of N,N-methylene bisacrylamide .
所述第一乳液聚合的条件包括：所述第一核共聚物区的共聚单体的总 浓度为9.24重量％，乳化剂(丁二酸二己酯磺酸钠和十二烷基苯磺酸钠的1：2.114的混合物)浓度为2.1重量％，分子量调节剂(叔十二硫醇)的浓度为0.027重量％，引发剂(过硫酸铵)的浓度为5.4重量％，螯合剂(EDTA)的浓度为0.054重量％，用水补足余量，聚合的时间为10分钟，聚合的温度为68℃。The conditions for the first emulsion polymerization include: the total amount of comonomers in the first core copolymer zone The concentration is 9.24% by weight, the emulsifier (a 1:2.114 mixture of sodium dihexyl succinate sulfonate and sodium dodecyl benzene sulfonate) concentration is 2.1% by weight, and the molecular weight regulator (tert-dodecyl mercaptan) The concentration of initiator (ammonium persulfate) is 5.4% by weight, the concentration of chelating agent (EDTA) is 0.054% by weight, the balance is made up with water, the polymerization time is 10 minutes, and the polymerization temperature is 68 ℃.
将所述第一核共聚物(以所述第一乳液聚合后所得的物料进行使用)与第一壳共聚物区的共聚单体进行第二乳液聚合，得到具有第一核壳结构的第一共聚物。The first core copolymer (used as a material obtained after the first emulsion polymerization) and the comonomer in the first shell copolymer region are subjected to a second emulsion polymerization to obtain the first core-shell structure. copolymer.
所述第一壳共聚物区的共聚单体包括37.2重量份的苯乙烯、53.53重量份的丁二烯、1.12重量份的衣康酸和0.22重量份的N,N-亚甲基双丙烯酰胺。The comonomers of the first shell copolymer zone include 37.2 parts by weight of styrene, 53.53 parts by weight of butadiene, 1.12 parts by weight of itaconic acid and 0.22 parts by weight of N,N-methylene bisacrylamide .
所述第二乳液聚合的条件包括：所述第一乳液聚合后所得的物料的用量为77.40重量％，所述第一壳共聚物区的共聚单体的用量为10.58重量％，乳化剂(丁二酸二己酯磺酸钠和十二烷基苯磺酸钠的1：1.158的混合物)浓度为0.186重量％，分子量调节剂(叔十二硫醇)的浓度为0.239重量％，引发剂(过硫酸铵)的浓度为3.98重量％，用水补足余量，聚合的时间为630分钟，聚合的温度为68℃。聚合结束后得到第二共聚物。The conditions for the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization is 77.40% by weight, the amount of comonomer in the first shell copolymer zone is 10.58% by weight, and the emulsifier (D The concentration of sodium dihexyl sulfonate and sodium dodecyl benzene sulfonate (1:1.158 mixture) is 0.186% by weight, the concentration of the molecular weight regulator (tert-dodecanethiol) is 0.239% by weight, and the initiator ( The concentration of ammonium persulfate (ammonium persulfate) was 3.98% by weight, and the balance was made up with water. The polymerization time was 630 minutes, and the polymerization temperature was 68°C. After the polymerization is completed, a second copolymer is obtained.
将第二核共聚物区的共聚单体进行第三乳液聚合，得到第二核共聚物。The comonomer in the second core copolymer region is subjected to third emulsion polymerization to obtain a second core copolymer.
所述第二核共聚物区的共聚单体包括8.575重量份的苯乙烯、25.725重量份的丙烯酸丁酯和3重量份的衣康酸；The comonomers of the second core copolymer zone include 8.575 parts by weight of styrene, 25.725 parts by weight of butyl acrylate, and 3 parts by weight of itaconic acid;
所述第三乳液聚合的条件包括：所述第二核共聚物区的共聚单体的总浓度为6.63重量％，乳化剂(十二烷基酚聚氧乙烯醚)浓度为0.58重量％，分子量调节剂(正十二硫醇)的浓度为0.066重量％，引发剂(过硫酸铵)的浓度为3.86重量％，用水补足余量，聚合的时间为15分钟，聚合的温度为69℃。The conditions for the third emulsion polymerization include: the total concentration of comonomers in the second core copolymer zone is 6.63% by weight, the concentration of the emulsifier (dodecylphenol polyoxyethylene ether) is 0.58% by weight, and the molecular weight The concentration of the regulator (n-dodecanethiol) was 0.066% by weight, the concentration of the initiator (ammonium persulfate) was 3.86% by weight, and the balance was made up with water. The polymerization time was 15 minutes, and the polymerization temperature was 69°C.
将所述第二核共聚物(以所述第三乳液聚合后所得的物料进行使用) 与第二壳共聚物区的共聚单体进行第四乳液聚合，得到具有第二核壳结构的第二共聚物。The second core copolymer (used as a material obtained after the third emulsion polymerization) The fourth emulsion polymerization is performed with the comonomer of the second shell copolymer region to obtain a second copolymer having a second core-shell structure.
所述第二壳共聚物区的共聚单体包括111重量份的苯乙烯、9.5重量份的丙烯酸丁酯、333重量份的丙烯酸和11.1重量份的N,N-亚甲基双丙烯酰胺。The comonomers of the second shell copolymer zone include 111 parts by weight of styrene, 9.5 parts by weight of butyl acrylate, 333 parts by weight of acrylic acid, and 11.1 parts by weight of N,N-methylene bisacrylamide.
所述第四乳液聚合的条件包括：所述第三乳液聚合后所得的物料的用量为56.93重量％，所述第一壳共聚物区的共聚单体的用量为7.49重量％，乳化剂(脂肪醇醚硫酸盐)浓度为0.29重量％，分子量调节剂(正十二硫醇)的浓度为0.086重量％，引发剂(过硫酸铵)的浓度为4.5重量％，螯合剂(EDTA)的浓度为4.5重量％，用水补足余量，聚合的时间为510分钟，聚合的温度为69℃。聚合结束后得到第二共聚物。The conditions for the fourth emulsion polymerization include: the amount of material obtained after the third emulsion polymerization is 56.93% by weight, the amount of comonomer in the first shell copolymer zone is 7.49% by weight, and the emulsifier (fat Alcohol ether sulfate) concentration is 0.29% by weight, the concentration of the molecular weight regulator (n-dodecanethiol) is 0.086% by weight, the concentration of the initiator (ammonium persulfate) is 4.5% by weight, and the concentration of the chelating agent (EDTA) is 4.5% by weight, the balance was made up with water, the polymerization time was 510 minutes, and the polymerization temperature was 69°C. After the polymerization is completed, a second copolymer is obtained.
将第一共聚物与第二共聚物按4.89:1的重量比进行混合，并调节固含量为40重量％，得到本实施例的粘结剂。The first copolymer and the second copolymer are mixed at a weight ratio of 4.89:1, and the solid content is adjusted to 40% by weight to obtain the adhesive of this embodiment.
实施例2Example 2
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按8:1的重量比进行混合。The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 8:1.
实施例3Example 3
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按2:1的重量比进行混合。The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 2:1.
实施例4Example 4
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按15:1的重量比进行混合。 The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 15:1.
实施例5Example 5
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按0.5:1的重量比进行混合。The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 0.5:1.
实施例6Example 6
按照实施例1的方式制备粘结剂；不同之处在于：将所述第一共聚物中的衣康酸替换为丙烯酸。The adhesive was prepared in the same manner as in Example 1; the difference was that the itaconic acid in the first copolymer was replaced with acrylic acid.
实施例7Example 7
按照实施例1的方式制备粘结剂；不同之处在于：将所述第一共聚物中的衣康酸替换为富马酸。The binder was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced with fumaric acid.
实施例8Example 8
按照实施例1的方式制备粘结剂；不同之处在于：将所述第一共聚物中的衣康酸替换为马来酸。The adhesive was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced with maleic acid.
实施例9Example 9
按照实施例1的方式制备粘结剂；不同之处在于：将所述第二共聚物中的丙烯酸丁酯替换为丙烯酸乙酯。The adhesive was prepared in the same manner as in Example 1; the difference was that butyl acrylate in the second copolymer was replaced with ethyl acrylate.
实施例10Example 10
按照实施例1的方式制备粘结剂；不同之处在于：将所述第二共聚物中的丙烯酸替换为衣康酸。The adhesive was prepared in the same manner as in Example 1; the difference was that the acrylic acid in the second copolymer was replaced by itaconic acid.
对比例1Comparative example 1
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按60:1的重量比进行混合。 The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 60:1.
对比例2Comparative example 2
按照实施例1的方式制备粘结剂；不同之处在于：将第一共聚物与第二共聚物按0.04:1的重量比进行混合。The adhesive was prepared in the same manner as in Example 1; the difference was that the first copolymer and the second copolymer were mixed at a weight ratio of 0.04:1.
对比例3Comparative example 3
按照实施例1的方式制备粘结剂；不同之处在于：将所述第一共聚物中的衣康酸替换为丙烯酰胺。The adhesive was prepared in the same manner as in Example 1; the difference was that itaconic acid in the first copolymer was replaced by acrylamide.
对比例4Comparative example 4
按照实施例1的方式制备粘结剂；不同之处在于：将所述第二共聚物中的丙烯酸丁酯替换为丙烯酰胺。The adhesive was prepared in the same manner as in Example 1; the difference was that butyl acrylate in the second copolymer was replaced with acrylamide.
测试实施例1Test Example 1
本测试实施例对实施例1-10和对比例1-4的粘结剂进行耐电解液浸泡测试。In this test example, the binders of Examples 1-10 and Comparative Examples 1-4 are subjected to an electrolyte immersion resistance test.
取70g稀释至20重量％固含的粘结剂，倾倒于模具内并移送至烤箱，依次在60℃烘烤8小时，90℃烘烤4小时，120℃烘烤2小时，140℃烘烤15分钟条件下，得到胶膜。然后将胶膜冲切成哑铃状，作为第一胶膜备用。将第一胶膜放入铝塑袋，注入胶膜重量40倍的电解液并封口。将封装好的铝塑袋移入40℃烘箱，烘烤15天。取出铝塑袋内胶膜，使用吸水纸吸干胶膜表面电解液，作为第二胶膜备用。再将第二胶膜在140℃烘箱内烘烤2小时，烘干胶膜内残余电解液，作为第三胶膜备用。Take 70g of the binder diluted to 20% by weight, pour it into the mold and transfer it to the oven. Bake at 60°C for 8 hours, 90°C for 4 hours, 120°C for 2 hours, and 140°C. Under the conditions of 15 minutes, a film was obtained. Then punch the film into a dumbbell shape and use it as the first film. Put the first plastic film into the aluminum plastic bag, inject electrolyte 40 times the weight of the film and seal it. Move the sealed aluminum plastic bag into a 40°C oven and bake for 15 days. Remove the adhesive film from the aluminum-plastic bag and use absorbent paper to absorb the electrolyte on the surface of the adhesive film and use it as a second adhesive film for later use. Then bake the second film in a 140°C oven for 2 hours to dry the residual electrolyte in the film and use it as a third film for later use.
对上述第一胶膜、第二胶膜和第三胶膜进行拉伸实验，结果表见表1-3。图1是实施例1的第二胶膜的照片，图2是实施例1的第一胶膜的照片。图3是对比例1的第二胶膜的照片，图4是对比例1的第一胶膜的照片。 可以明显看出，对比例1的胶膜在电解液浸泡后颜色呈棕色，而实施例1的胶膜在电解液浸泡后颜色无明显变化。由此说明实施例1的胶膜具有优异的电解液浸泡耐受性。A tensile test was performed on the above-mentioned first rubber film, second rubber film and third rubber film. The results are shown in Table 1-3. FIG. 1 is a photograph of the second adhesive film of Example 1, and FIG. 2 is a photograph of the first adhesive film of Example 1. FIG. 3 is a photograph of the second adhesive film of Comparative Example 1, and FIG. 4 is a photograph of the first adhesive film of Comparative Example 1. It can be clearly seen that the color of the rubber film of Comparative Example 1 turned brown after being soaked in electrolyte, while the color of the rubber film of Example 1 did not change significantly after being soaked in electrolyte. This shows that the adhesive film of Example 1 has excellent electrolyte immersion resistance.
表1第一胶膜测试结果
Table 1 First film test results
表2第二胶膜测试结果
Table 2 Second film test results
表3第三胶膜测试结果
Table 3 Third adhesive film test results
通过表1-表3的结果可以看出，本发明的粘结剂所形成的胶膜受电解液浸泡影响较小。It can be seen from the results in Tables 1 to 3 that the adhesive film formed by the adhesive of the present invention is less affected by electrolyte immersion.
测试实施例2Test Example 2
本测试实施例对实施例1-10和对比例1-4的粘结剂进行剥离强度(集流体粘合度)测试。In this test example, the adhesives of Examples 1-10 and Comparative Examples 1-4 were tested for peel strength (current collector adhesion).
将本发明按1.4重量％和1.7重量％的添加量加入负极浆料，然后制浆、涂布、干燥、滚压后得到极片，将极片冲切成20mm宽长条，在万能拉力试验机上采用90度剥离的方法进行测试。结果如表4所示。The present invention is added to the negative electrode slurry in an amount of 1.4% by weight and 1.7% by weight, and then pulped, coated, dried, and rolled to obtain a pole piece. The pole piece is punched into 20mm wide strips and tested in a universal tensile test. The 90-degree peeling method is used for testing on the machine. The results are shown in Table 4.
表4剥离强度测试结果

Table 4 Peel strength test results

通过表4的结果可以看出，本发明的粘结剂固化后的剥离强度较高。It can be seen from the results in Table 4 that the adhesive of the present invention has higher peel strength after curing.
测试实施例3Test Example 3
本测试实施例对实施例1-10和对比例1-4的粘结剂制备电池，并进行电池循环性能测试。In this test example, batteries were prepared using the binders of Examples 1-10 and Comparative Examples 1-4, and battery cycle performance tests were conducted.
电池使用软包叠片5AH来评估，正极使用容量型LFP，负极使用类FSN人造石墨，CMC加入量在1.2％，电池设计参考能量型电池设计方法进行110周常温1C、55℃1C测试。结果如表5所示。The battery was evaluated using soft-pack laminates 5AH. The positive electrode used capacity-type LFP and the negative electrode used FSN-like artificial graphite. The CMC addition amount was 1.2%. The battery design was conducted with reference to the energy battery design method for 110 weeks of normal temperature 1C and 55°C 1C tests. The results are shown in Table 5.
表5电池循环性能测试结果
Table 5 Battery cycle performance test results
通过表5的结果可以看出，本发明的粘结剂的制备出的电池的循环性能较好。It can be seen from the results in Table 5 that the battery prepared with the binder of the present invention has better cycle performance.
通过上述测试实施例可以看到，本发明的用于锂离子电池负极的粘结剂能够在成膜后具有优异的电解液耐受性，从而可以有效地提高锂离子电池的性能，特别是优选所述第一共聚物与所述第二共聚物的重量比为0.5-15:1，优选为2-8:1，更优选为4.5-5.5:1的情况下，所述粘结剂具有更好的性能。It can be seen from the above test examples that the binder for lithium-ion battery negative electrodes of the present invention can have excellent electrolyte tolerance after film formation, thereby effectively improving the performance of lithium-ion batteries, and is particularly preferred. When the weight ratio of the first copolymer to the second copolymer is 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1, the binder has more good performance.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner as long as there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (11)

  1. 一种用于锂离子电池负极的粘结剂，其特征在于，该粘结剂包括第一共聚物和第二共聚物；所述第一共聚物与所述第二共聚物的重量比为0.05-50:1；A binder for the negative electrode of lithium ion battery, characterized in that the binder includes a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 0.05 -50:1;
    所述第一共聚物具有第一核壳结构并含有第一核共聚物区和第一壳共聚物区；所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；The first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer region includes 0.1-20 parts by weight of a monovinyl group Aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.01-20 parts by weight of bisacrylamide monomers; the first shell is copolymerized The comonomers in the material zone include 1-60 parts by weight of monovinyl aromatic compounds, 1-100 parts by weight of aliphatic conjugated dienes, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomers and 0.01-20 parts by weight of monovinyl aromatic compounds. 20 parts by weight of bisacrylamide monomer;
    所述第二共聚物具有第二核壳结构并含有第二核共聚物区和第二壳共聚物区；所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。The second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; the comonomer of the second core copolymer region includes 0.1-20 parts by weight of a monovinyl group Aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers; the comonomers of the second shell copolymer zone include 0.1-200 parts by weight of monomers Vinyl aromatic compound, 0.1-500 parts by weight of acrylate monomer, 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
  2. 根据权利要求1所述的粘结剂，其中，优选所述第一共聚物与所述第二共聚物的重量比为0.5-15:1，优选为2-8:1，更优选为4.5-5.5:1；The adhesive according to claim 1, wherein the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, and more preferably 4.5- 5.5:1;
    所述第一共聚物中，所述第一核共聚物区和第一壳共聚物区的重量比为0.01-20:1，优选为0.1-10:1，更优选为0.3-5:1；In the first copolymer, the weight ratio of the first core copolymer region and the first shell copolymer region is 0.01-20:1, preferably 0.1-10:1, and more preferably 0.3-5:1;
    所述第二共聚物中，所述第二核共聚物区和第二壳共聚物区的重量比为0.01-50:1，优选为0.1-30:1，更优选为0.3-5:1。In the second copolymer, the weight ratio of the second core copolymer region and the second shell copolymer region is 0.01-50:1, preferably 0.1-30:1, and more preferably 0.3-5:1.
  3. 根据权利要求1所述的粘结剂，其中，所述第一共聚物的聚合物粒子的粒径在50-1000nm之间，所述第一共聚物的玻璃化温度为-40℃至90℃；所述第二共聚物的聚合物粒子的粒径在50-1000nm之间，所述第二共聚物 的玻璃化温度为-40℃至90℃；The binder according to claim 1, wherein the particle size of the polymer particles of the first copolymer is between 50-1000 nm, and the glass transition temperature of the first copolymer is -40°C to 90°C. ; The particle size of the polymer particles of the second copolymer is between 50-1000nm, and the second copolymer The glass transition temperature is -40℃ to 90℃;
    所述粘结剂的固含量为10-60重量％。The solid content of the binder is 10-60% by weight.
  4. 根据权利要求1-3中任意一项所述的粘结剂，其中，所述单乙烯基芳香族化合物各自独立地为苯乙烯、邻位甲基苯乙烯、间位甲基苯乙烯和对位甲基苯乙烯中的至少一种；所述脂肪族共轭二烯烃各自独立地为1,3-丁二烯和/或异戊二烯；所述水溶性不饱和羧酸各自独立地为甲基丙烯酸、丙烯酸、衣康酸、富马酸和马来酸中的至少一种；所述双丙烯酰胺单体各自独立地为N,N-亚甲基双丙烯酰胺、N,N-(1,2-二羟基乙烯)双丙烯酰胺和酒石酸双丙烯酰胺中的至少一种；所述丙烯酸酯单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯和丙烯酸戊酯中的至少一种；The adhesive according to any one of claims 1 to 3, wherein the monovinyl aromatic compounds are each independently styrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene. At least one of methylstyrene; the aliphatic conjugated diene is each independently 1,3-butadiene and/or isoprene; the water-soluble unsaturated carboxylic acid is each independently methane At least one of acrylic acid, acrylic acid, itaconic acid, fumaric acid and maleic acid; the bisacrylamide monomers are each independently N,N-methylene bisacrylamide, N,N-(1 , 2-dihydroxyethylene) at least one of bisacrylamide and tartrate bisacrylamide; the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate. A sort of;
    优选地，所述单乙烯基芳香族化合物为苯乙烯，所述脂肪族共轭二烯烃为1,3-丁二烯，所述第一核共聚物区、所述第一壳共聚物区和所述第二核共聚物区中的所述水溶性不饱和羧酸为衣康酸，所述第二壳共聚物区中的所述水溶性不饱和羧酸为丙烯酸和/或甲基丙烯酸，所述双丙烯酰胺单体为N,N-亚甲基双丙烯酰胺，所述丙烯酸酯单体为丙烯酸丁酯。Preferably, the monovinyl aromatic compound is styrene, the aliphatic conjugated diene is 1,3-butadiene, the first core copolymer region, the first shell copolymer region and The water-soluble unsaturated carboxylic acid in the second core copolymer region is itaconic acid, and the water-soluble unsaturated carboxylic acid in the second shell copolymer region is acrylic acid and/or methacrylic acid, The bisacrylamide monomer is N,N-methylene bisacrylamide, and the acrylate monomer is butyl acrylate.
  5. 一种制备用于锂离子电池负极的粘结剂的方法，其特征在于，该方法包括：A method of preparing a binder for a lithium-ion battery negative electrode, characterized in that the method includes:
    将第一核共聚物区的共聚单体进行第一乳液聚合，得到第一核共聚物；Performing first emulsion polymerization on the comonomer in the first core copolymer zone to obtain the first core copolymer;
    将所述第一核共聚物与第一壳共聚物区的共聚单体进行第二乳液聚合，得到具有第一核壳结构的第一共聚物；Perform second emulsion polymerization of the comonomers of the first core copolymer and the first shell copolymer region to obtain a first copolymer with a first core-shell structure;
    将第二核共聚物区的共聚单体进行第三乳液聚合，得到第二核共聚物；Perform third emulsion polymerization on the comonomer in the second core copolymer region to obtain a second core copolymer;
    将所述第二核共聚物与第二壳共聚物区的共聚单体进行第四乳液聚合，得到具有第二核壳结构的第二共聚物；Perform fourth emulsion polymerization of the comonomers in the second core copolymer and the second shell copolymer region to obtain a second copolymer with a second core-shell structure;
    将第一共聚物与第二共聚物按0.05-50:1的重量比进行混合；Mix the first copolymer and the second copolymer in a weight ratio of 0.05-50:1;
    所述第一核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-20重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和 羧酸单体和0.01-20重量份的双丙烯酰胺单体；所述第一壳共聚物区的共聚单体包括1-60重量份的单乙烯基芳香族化合物、1-100重量份的脂肪族共轭二烯烃、0.01-20重量份的水溶性不饱和羧酸单体和0.01-20重量份的双丙烯酰胺单体；The comonomers of the first core copolymer zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-20 parts by weight of aliphatic conjugated dienes, and 0.01-20 parts by weight of water-soluble unsaturated Carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer; the comonomers of the first shell copolymer region include 1-60 parts by weight of monovinyl aromatic compounds and 1-100 parts by weight of fat Conjugated diene, 0.01-20 parts by weight of water-soluble unsaturated carboxylic acid monomer and 0.01-20 parts by weight of bisacrylamide monomer;
    所述第二核共聚物区的共聚单体包括0.1-20重量份的单乙烯基芳香族化合物、0.1-50重量份的丙烯酸酯单体和0.1-20重量份的水溶性不饱和羧酸单体；所述第二壳共聚物区的共聚单体包括0.1-200重量份的单乙烯基芳香族化合物、0.1-500重量份的丙烯酸酯单体、0.1-20重量份的水溶性不饱和羧酸单体和0.1-20重量份的双丙烯酰胺单体。The comonomers of the second core copolymer zone include 0.1-20 parts by weight of monovinyl aromatic compounds, 0.1-50 parts by weight of acrylate monomers and 0.1-20 parts by weight of water-soluble unsaturated carboxylic acid monomers. body; the comonomers of the second shell copolymer region include 0.1-200 parts by weight of monovinyl aromatic compounds, 0.1-500 parts by weight of acrylic ester monomers, and 0.1-20 parts by weight of water-soluble unsaturated carboxyl acid monomer and 0.1-20 parts by weight of bisacrylamide monomer.
  6. 根据权利要求5所述的方法，其中，优选所述第一共聚物与所述第二共聚物的重量比为0.5-15:1，优选为2-8:1，更优选为4.5-5.5:1。The method according to claim 5, wherein the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, and more preferably 4.5-5.5: 1.
  7. 根据权利要求5所述的方法，其中，The method of claim 5, wherein
    所述第一乳液聚合的条件包括：所述第一核共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.01-10重量％，分子量调节剂的浓度为0.001-5重量％，引发剂的浓度为0.001-20重量％，螯合剂的浓度为0.01-10重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃；The conditions for the first emulsion polymerization include: the total concentration of comonomers in the first core copolymer zone is 1-30% by weight, the concentration of the emulsifier is 0.01-10% by weight, and the concentration of the molecular weight regulator is 0.001- 5% by weight, the concentration of the initiator is 0.001-20% by weight, the concentration of the chelating agent is 0.01-10% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C;
    所述第二乳液聚合的条件包括：所述第一乳液聚合后所得的物料的用量为0.1-90重量％，所述第一壳共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.01-10重量％，分子量调节剂的浓度为0.001-5重量％，引发剂的浓度为0.001-20重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃；The conditions for the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization is 0.1-90% by weight, and the total concentration of comonomers in the first shell copolymer zone is 1-30% by weight. , the concentration of emulsifier is 0.01-10% by weight, the concentration of molecular weight regulator is 0.001-5% by weight, the concentration of initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90 ℃;
    所述第三乳液聚合的条件包括：所述第二核共聚物区的共聚单体的总浓度为0.1-90重量％，乳化剂浓度为0.001-20重量％，分子量调节剂的浓度为0.001-20重量％，引发剂的浓度为0.001-20重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃；The conditions for the third emulsion polymerization include: the total concentration of comonomers in the second core copolymer zone is 0.1-90% by weight, the concentration of the emulsifier is 0.001-20% by weight, and the concentration of the molecular weight regulator is 0.001-20% by weight. 20% by weight, the concentration of the initiator is 0.001-20% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C;
    所述第四乳液聚合的条件包括：所述第三乳液聚合后所得的物料的用量为 1-85重量％，所述第一壳共聚物区的共聚单体的总浓度为1-30重量％，乳化剂浓度为0.001-20重量％，分子量调节剂的浓度为0.001-20重量％，引发剂的浓度为0.001-20重量％，螯合剂的浓度为0.01-10重量％，聚合的时间为1-1000分钟，聚合的温度为30-90℃；The conditions for the fourth emulsion polymerization include: the amount of material obtained after the third emulsion polymerization is 1-85% by weight, the total concentration of comonomers in the first shell copolymer zone is 1-30% by weight, the concentration of the emulsifier is 0.001-20% by weight, and the concentration of the molecular weight regulator is 0.001-20% by weight, The concentration of the initiator is 0.001-20% by weight, the concentration of the chelating agent is 0.01-10% by weight, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90°C;
    所述乳化剂各自独立地选自丁二酸二己酯磺酸钠、十二烷基苯磺酸钠、脂肪醇醚硫酸盐、十二烷基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、仲烷基磺酸钠、烷基二苯醚二磺酸盐和脂肪族羧酸盐中的至少一种；The emulsifiers are each independently selected from the group consisting of sodium dihexyl sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol ether sulfate, dodecylphenol polyoxyethylene ether, and octylphenol polyoxyethylene. At least one of ether, sodium secondary alkyl sulfonate, alkyl diphenyl ether disulfonate and aliphatic carboxylate;
    所述分子量调节剂各自独立地选自正十二硫醇、叔十二硫醇、二硫化二异丙基黄原酸酯和α-甲基苯乙烯线性二聚体中的至少一种；The molecular weight regulator is each independently selected from at least one of n-dodecanethiol, tert-dodecanethiol, diisopropyl xanthate disulfide and α-methylstyrene linear dimer;
    所述引发剂各自独立地为过硫酸钾、过硫酸钠、过硫酸铵、叔丁基过氧化氢、过氧化苯甲酰和乙酰化过氧化氢中的至少一种。The initiators are each independently at least one of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, benzoyl peroxide and acetylated hydrogen peroxide.
  8. 权利要求5-7中任意一项所述的方法制备得到的粘结剂。The adhesive prepared by the method described in any one of claims 5-7.
  9. 权利要求1-4和8中任意一项所述的粘结剂在制备锂离子电池负极中的用途。Use of the binder described in any one of claims 1-4 and 8 in the preparation of negative electrodes for lithium ion batteries.
  10. 一种锂离子电池负极，其特征在于，所述锂离子电池负极含有权利要求1-4和8中任意一项所述的粘结剂。A lithium ion battery negative electrode, characterized in that the lithium ion battery negative electrode contains the binder described in any one of claims 1-4 and 8.
  11. 一种锂离子电池，其特征在于，所述锂离子电池含有正极、电解液和负极；所述负极为权利要求10所述的负极。 A lithium ion battery, characterized in that the lithium ion battery contains a positive electrode, an electrolyte and a negative electrode; the negative electrode is the negative electrode according to claim 10.
PCT/CN2023/103478 2022-06-29 2023-06-28 Binder for negative electrode of lithium-ion battery, and preparation method therefor and use thereof WO2024002199A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210764529.5A CN115050963B (en) 2022-06-29 2022-06-29 Adhesive for negative electrode of lithium ion battery, and preparation method and application thereof
CN202210764529.5 2022-06-29

Publications (1)

Publication Number Publication Date
WO2024002199A1 true WO2024002199A1 (en) 2024-01-04

Family

ID=83164530

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/103478 WO2024002199A1 (en) 2022-06-29 2023-06-28 Binder for negative electrode of lithium-ion battery, and preparation method therefor and use thereof

Country Status (2)

Country Link
CN (1) CN115050963B (en)
WO (1) WO2024002199A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115050963B (en) * 2022-06-29 2024-05-10 上海道赢实业有限公司 Adhesive for negative electrode of lithium ion battery, and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180108912A1 (en) * 2015-06-17 2018-04-19 Lg Chem, Ltd. Binder composition for secondary batteries, and electrode and lithium secondary battery including the same
CN111825804A (en) * 2020-07-27 2020-10-27 日照广大建筑材料有限公司 Copolymer latex for lithium ion secondary battery cathode, preparation method and application
CN113555558A (en) * 2021-07-12 2021-10-26 珠海冠宇电池股份有限公司 Emulsion type binder and lithium ion battery comprising same
CN114520329A (en) * 2020-11-19 2022-05-20 比亚迪股份有限公司 Adhesive, preparation method thereof and slurry
CN114583173A (en) * 2022-03-15 2022-06-03 湖北亿纬动力有限公司 Negative electrode slurry composition and application
CN115050963A (en) * 2022-06-29 2022-09-13 上海道赢实业有限公司 Binder for lithium ion battery cathode and preparation method and application thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0113995A (en) * 2000-09-21 2003-08-12 Rohm & Haas Process for preparing a nanocomposite polymeric aqueous clay dispersion, plastic additive product, nanocomposite powder product, thermoplastic resin or plastic additive, core-shell nanocomposite polymeric composition, and coating, adhesive, caulking or sealant product
CN103173161B (en) * 2013-03-08 2016-08-03 东莞新能源科技有限公司 A kind of preparation method of lithium ion battery cathode sheet adhesive emulsion
JP2014203805A (en) * 2013-04-10 2014-10-27 日本ゼオン株式会社 Particulate binder for lithium ion secondary battery negative electrode, slurry composition for lithium ion secondary battery negative electrode, and lithium ion secondary battery
KR101597745B1 (en) * 2013-05-23 2016-02-25 주식회사 엘지화학 Binder for Secondary Battery and Secondary Battery Comprising the Same
WO2015160794A1 (en) * 2014-04-14 2015-10-22 Ecosynthetix Ltd. Bio-based nanoparticle and composite materials derived therefrom
CN106663813B (en) * 2014-09-05 2020-12-08 日本瑞翁株式会社 Binder composition for secondary battery electrode, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery
KR101698745B1 (en) * 2015-08-03 2017-01-23 주식회사 한솔케미칼 Core-shell structured binders for use of anode materials of lithium ion secondary battery and method for preparing using the same, and slurry comprising said binders
KR20180059433A (en) * 2015-09-28 2018-06-04 니폰 제온 가부시키가이샤 A binder composition for a non-aqueous secondary battery electrode, a slurry composition for a non-aqueous secondary battery electrode, an electrode for a non-aqueous secondary battery,
CN108929401A (en) * 2018-06-25 2018-12-04 重庆云天化瀚恩新材料开发有限公司 A kind of lithium battery silicium cathode adhesive and preparation method thereof
KR102306446B1 (en) * 2018-12-28 2021-09-28 삼성에스디아이 주식회사 Separator for rechargeable lithium battery and rechargeable lithium battery including the same
KR20220087853A (en) * 2020-12-18 2022-06-27 주식회사 엘지화학 Electrode binder composition for rechargeable battery and electrode mixture including the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180108912A1 (en) * 2015-06-17 2018-04-19 Lg Chem, Ltd. Binder composition for secondary batteries, and electrode and lithium secondary battery including the same
CN111825804A (en) * 2020-07-27 2020-10-27 日照广大建筑材料有限公司 Copolymer latex for lithium ion secondary battery cathode, preparation method and application
CN114520329A (en) * 2020-11-19 2022-05-20 比亚迪股份有限公司 Adhesive, preparation method thereof and slurry
CN113555558A (en) * 2021-07-12 2021-10-26 珠海冠宇电池股份有限公司 Emulsion type binder and lithium ion battery comprising same
CN114583173A (en) * 2022-03-15 2022-06-03 湖北亿纬动力有限公司 Negative electrode slurry composition and application
CN115050963A (en) * 2022-06-29 2022-09-13 上海道赢实业有限公司 Binder for lithium ion battery cathode and preparation method and application thereof

Also Published As

Publication number Publication date
CN115050963A (en) 2022-09-13
CN115050963B (en) 2024-05-10

Similar Documents

Publication Publication Date Title
CN104981927B (en) Adhesive for secondary cell and the secondary cell comprising the adhesive
JP5547507B2 (en) Nonaqueous electrolyte secondary battery electrode binder.
WO2018032665A1 (en) Acrylonitrile copolymer adhesive and use of same in lithium ion battery
JP3721727B2 (en) Battery electrode binder
JP5259373B2 (en) Nonaqueous electrolyte secondary battery electrode binder
WO2024002199A1 (en) Binder for negative electrode of lithium-ion battery, and preparation method therefor and use thereof
JP3710826B2 (en) Polymer dispersion composition
WO2020168942A1 (en) Crosslinked sbr microsphere binder, preparation method, and lithium-ion battery containing said binder
WO2019242318A1 (en) Waterborne binder, preparation method therefor and use thereof
WO2022111580A1 (en) Dispersant for lithium ion battery, preparation method therefor, positive electrode slurry and lithium ion battery
CN106797032A (en) Adhesive composition for secondary cell and the electrode comprising it and lithium secondary battery
CN108172837A (en) Lithium ion battery negative material, anode plate for lithium ionic cell and preparation method thereof and lithium ion battery
WO2001029917A1 (en) Binder composition for electrodes of lithium ion secondary batteries and use thereof
KR20090019630A (en) Binder for secondary battery comprising copolymer of vinyl acetate or vinyl alcohol
JP4438102B2 (en) Binder for battery, slurry for battery electrode, electrode for lithium secondary battery, and lithium secondary battery
CN115332540B (en) Negative electrode binder for secondary battery and preparation method thereof
JPH09199135A (en) Binder composition for battery, electrode and battery
JP5651346B2 (en) Battery electrode composition
JP4438104B2 (en) Secondary battery binder composition, battery electrode slurry, battery electrode, and secondary battery
CN111969211A (en) Negative plate of lithium ion battery capable of being rapidly charged at low temperature, lithium ion battery and preparation method
CN115044331B (en) Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof
JP6029823B2 (en) Aqueous composition for secondary battery electrode and electrode for secondary battery positive electrode
JP2014123550A (en) Aqueous binder for battery electrode and method for producing the same
CN113964309B (en) Negative electrode slurry and preparation method thereof, negative electrode plate and secondary battery
CN108232112A (en) Lithium ion battery negative material, anode plate for lithium ionic cell and preparation method thereof and lithium ion battery

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23830370

Country of ref document: EP

Kind code of ref document: A1