WO2024000100A1 - 粘结剂及其应用 - Google Patents

粘结剂及其应用 Download PDF

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Publication number
WO2024000100A1
WO2024000100A1 PCT/CN2022/101486 CN2022101486W WO2024000100A1 WO 2024000100 A1 WO2024000100 A1 WO 2024000100A1 CN 2022101486 W CN2022101486 W CN 2022101486W WO 2024000100 A1 WO2024000100 A1 WO 2024000100A1
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Prior art keywords
optionally
alkyl
acrylate
formula
binder
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PCT/CN2022/101486
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English (en)
French (fr)
Inventor
杨丙梓
程丛
陈均桄
裴海乐
张盛武
王星会
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宁德时代新能源科技股份有限公司
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Priority to CN202280014080.9A priority Critical patent/CN117642890A/zh
Priority to PCT/CN2022/101486 priority patent/WO2024000100A1/zh
Publication of WO2024000100A1 publication Critical patent/WO2024000100A1/zh

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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
    • 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

Definitions

  • the present application relates to the technical field of secondary batteries, and in particular to a binder, a slurry containing the binder and its related electrode plates, secondary batteries, battery modules, battery packs and electrical devices.
  • secondary batteries In recent years, the application range of secondary batteries has become more and more extensive. For example, it can be used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, Aerospace and other fields. With the widespread application of secondary batteries, people have higher and higher requirements for battery performance.
  • the adhesives used to prepare battery pole pieces in the prior art have insufficient adhesion, low cohesion, and a high swelling ratio of the formed adhesive film, making the pole pieces prone to cracking, curling, and cracking during the drying process.
  • the resulting pole pieces have poor brittleness and other problems, which seriously affect the electrical performance of the secondary battery.
  • This application was made in view of the above problems, and its purpose is to provide a binder, a slurry containing the binder and related electrode pole pieces, secondary batteries, battery modules, battery packs and electricity consumption
  • the device aims to improve the electrical performance of secondary batteries by ameliorating problems arising from the use of prior art binders.
  • the first aspect of the present application provides a binder, which includes a graft polymer, the graft polymer includes a copolymer of formula I as a main chain and a copolymer of formula I grafted on the main chain.
  • R 1 , R 2 and R 3 are each independently selected from at least one of hydrogen and C1-C6 alkyl, optionally each is independently selected from at least one of hydrogen and methyl;
  • R 6 is selected from at least one of COOH, OH, CN and carbonyloxy C1-C6 alkyl hydroxyl, optionally selected from at least one of OH and carbonyloxy C1-C6 alkyl hydroxyl;
  • x and y are each independently an integer from 0 to 5000, optionally an integer from 500 to 1500; x and y are not 0 at the same time;
  • z is an integer from 100 to 3000, optionally an integer from 200 to 1500;
  • R 7 is selected from C1-C6 alkenyl, C1-C6 alkynyl, C1-C6 alkyl azide, C1-C6 alkylamino, C1-C6 alkylcarboxy, C1-C6 alkylhydroxy, C1-C6 At least one of alkyl epoxy and C1-C6 alkyl mercapto, optionally selected from at least one of C1-C6 alkylamino, C1-C6 alkylcarboxy and C1-C6 alkyl epoxy;
  • R 10 is C1-C6 alkyl.
  • the copolymer of Formula I is a terpolymer formed by copolymerization of three monomers, wherein the first monomer is lithium (meth)acrylate, sodium (meth)acrylate or acrylonitrile; The second monomer is C1-C6 alkyl (meth)acrylate, (meth)acrylamide or acrylonitrile; the third monomer is hydroxy C1-C6 alkyl (meth)acrylate.
  • the molar ratio of the first monomer, the second monomer and the third monomer is (0.5-3): (0.5-2): 1, optionally (0.8-2.5): (0.6- 1.5):1.
  • the terpolymer is selected from the group consisting of poly(lithium acrylate-methyl acrylate-hydroxymethyl acrylate), poly(lithium acrylate-propyl acrylate-hydroxymethyl acrylate), poly(lithium acrylate-acrylic acid Amyl ester-hydroxymethyl acrylate), poly(lithium acrylate-acrylamide-hydroxymethyl acrylate), poly(acrylonitrile-methyl acrylate-hydroxymethyl acrylate) and poly(sodium acrylate-acrylonitrile-hydroxymethyl acrylate) ) at least one of the following.
  • the siloxane of Formula II is selected from at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltripropoxysilane. A sort of.
  • the binder is in the form of an aqueous emulsion, wherein the weight percent of the graft polymer in the aqueous emulsion is from 5% to 50%, optionally from 10% to 40%.
  • the second aspect of the application provides a method for preparing the adhesive described in the first aspect of the application, wherein the method includes the following steps:
  • Step (1) react the copolymer of formula I with a halogenated C1-C6 alkyl epoxy compound in the presence of a base, and the reaction is performed in the presence of a solvent;
  • Step (2) After optionally removing the solvent and adding water, the siloxane of formula II and optionally the surfactant are added and stirred.
  • the weight ratio of the copolymer of Formula I to the halogenated C1-C6 alkyl epoxy compound is 1: (0.005-0.1), optionally 1: (0.01-0.05).
  • the molar ratio of the halogenated C1-C6 alkyl epoxy compound to the siloxane of formula II is 1: (0.5-2), optionally 1: (0.8-1.5), and also The optional value is 1: (0.9-1.2).
  • the halogenated C1-C6 alkyl epoxy compound is epichlorohydrin
  • the base is selected from at least one of sodium hydride and sodium hydroxide, optionally sodium hydride;
  • the molar ratio of the halogenated C1-C6 alkyl epoxy compound to the base is 1:(0.5-2), optionally 1:(0.8-1.5), or optionally 1:(0.9-1.2)1.
  • the third aspect of the present application provides a slurry, which contains the adhesive described in the first aspect of the present application or the adhesive prepared according to the method described in the second aspect of the present application.
  • the slurry contains 0.5% to 5% by weight of the binder.
  • a fourth aspect of the present application provides an electrode pole piece, which includes a current collector and a film layer formed of the slurry described in the third aspect of the present application and disposed on at least one surface of the current collector.
  • the fifth aspect of the present application provides a secondary battery, which includes the electrode pole piece described in the fourth aspect of the present application.
  • a sixth aspect of the present application provides a battery module including the secondary battery of the fifth aspect of the present application.
  • a seventh aspect of the present application provides a battery pack, including the battery module of the sixth aspect of the present application.
  • An eighth aspect of the present application provides an electrical device, including at least one selected from the secondary battery of the fifth aspect of the present application, the battery module of the sixth aspect of the present application, or the battery pack of the seventh aspect of the present application. kind.
  • the adhesive of the present application has good bonding performance, high cohesion, low swelling rate of the formed adhesive film, and the pole piece prepared by it is not prone to problems such as cracking and curling during the drying process.
  • the secondary battery also has a good capacity retention rate.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 4 .
  • FIG. 6 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Figure 7 is an infrared spectrum of the grafted polymer in Example 1 of the present application, in which the characteristic peak at 1087 cm -1 indicates that the copolymer is grafted with a siloxane compound.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • the inventor found that when using binders in the prior art, especially poly(meth)acrylic acid water-based binders, the positive electrode sheets prepared therefrom have high brittleness, poor flexibility, low cohesion, and Problems such as high swelling coefficient in electrolyte.
  • the inventor unexpectedly found that after grafting a compound containing silicone onto a poly(meth)acrylic polymer, the resulting adhesive can significantly improve the above problems. This improvement is particularly beneficial for applications requiring thick coatings and high compaction densities.
  • the inventor believes that when the adhesive of the present application is used in the preparation of aqueous slurry, during the process of coating the slurry on the current collector and drying, the solvent in the slurry is drying. are taken away during the process, resulting in a gradual increase in the concentration of the binder, an increase in the concentration of silicone hydroxyl groups formed by hydrolysis of the grafted siloxane on each main chain, and an increase in the contact probability between silicone hydroxyl groups.
  • the two adjacent silanol groups are dehydrated during drying to form Si-O-Si covalent bonds, resulting in a strong irreversible cross-linked network, which improves the cohesive energy of the active material in the pole piece and enhances the active material and conductive agent.
  • the silicone hydroxyl groups in the adhesive can form Si-O-R covalent bonds with the hydroxyl groups in the current collector during the drying and dehydration process, which improves the adhesion between the active material and the current collector. connection strength.
  • the main chain is grafted with siloxane, it can be hydrolyzed under acidic, alkaline and other conditions to form silanol groups. Weak hydrogen bonding interactions are formed between the silanol groups of each molecular chain, making the adhesive more stable in the slurry.
  • Reversible cross-linking occurs in the material. This reversible cross-linking can gel the positive and negative electrode slurries during the resting process, preventing different internal components from floating or settling due to different densities, improving the stability and uniformity of the slurry, and prolonging the slurry. The storage time of the material.
  • the weak hydrogen bond interaction can only produce extremely low interaction forces and minimal shear in the outside world.
  • the hydrogen bond interaction can be destroyed under the action of force, resulting in reversible cross-linking rupture, and the slurry recovers its original fluidity and rheological properties, giving the slurry better processability.
  • the first aspect of the present application provides a binder, which includes a graft polymer including a copolymer of formula I as a main chain and a copolymer of formula II grafted on the main chain.
  • R 6 is selected from at least one of COOH, OH, CN and carbonyloxy C1-C6 alkyl hydroxyl, optionally selected from at least one of OH and carbonyloxy C1-C6 alkyl hydroxyl;
  • x and y are each independently an integer from 0 to 5000, and can optionally be an integer from 100 to 4000, or an integer from 200 to 3000, and further optionally an integer from 500 to 1500; x and y are not both at the same time 0;
  • z is an integer from 100 to 3000, and can be an integer from 150 to 2500, or an integer from 180 to 2000, or an integer from 200 to 1500;
  • R 7 is selected from C1-C6 alkenyl, C1-C6 alkynyl, C1-C6 alkyl azide, C1-C6 alkylamino, C1-C6 alkylcarboxy, C1-C6 alkylhydroxy, C1-C6 At least one of alkyl epoxy and C1-C6 alkyl mercapto, optionally selected from at least one of C1-C6 alkylamino, C1-C6 alkylcarboxy and C1-C6 alkyl epoxy;
  • R 8 and R 9 are each independently selected from at least one of C1-C6 alkyl and C1-C6 alkyloxy;
  • R 10 is C1-C6 alkyl.
  • C1-C6 alkyl refers to a straight-chain or branched-chain hydrocarbon with 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl base, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl Methylbutyl, 2,2-dimethylbutyl,
  • alkyl groups having 1 to 4 carbon atoms such as, inter alia, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • the number average molecular weight of the graft polymer ranges from 50,000 to 1,000,000, optionally from 100,000 to 800,000, and optionally from 150,000 to 600,000.
  • the weight percentage of the copolymer of Formula I in the graft polymer is 90% to 99.9%, optionally 90.5% to 98.5%, further optionally 91% to 98% , based on the total weight of the graft polymer.
  • the weight percentage of the siloxane of formula II in the graft polymer is 0.1% to 10%, optionally 0.5% to 8%, and optionally 1% to 6%, based on the Based on total weight of grafted polymer.
  • the number average molecular weight of the copolymer of Formula I ranges from 20,000 to 500,000, optionally from 50,000 to 400,000, and optionally from 100,000 to 350,000.
  • the relative molecular weight of the siloxane of Formula II is 50 to 500, optionally 100 to 400, and optionally 150 to 350.
  • the number average molecular weight is measured by gel permeation chromatography (GPC) method in accordance with GB/T 21863-2008 "Gel permeation chromatography (GPC) using tetrahydrofuran as eluent".
  • the grafting proportion of the siloxane of formula II in the graft polymer is 0.1 to 5%, optionally 0.5 to 3.5%, further optionally 0.8% to 3%.
  • the expression "grafting ratio” is understood to mean the ratio of the molar amount of grafted comonomers to the molar amount of total comonomers in the graft polymer.
  • the reaction between the copolymer of formula I and the siloxane of formula II can be carried out directly.
  • the copolymer of formula I contains branches that can react with the siloxane of formula II. Alkenyl, alkynyl, azido, amino, carboxyl, hydroxyl, epoxy or thiol groups directly react with the group; when the copolymer of formula I cannot directly react with the siloxane compound of formula II, The copolymer of formula I can be reacted with an intermediate compound first, and then reacted with the siloxane of formula II, wherein the intermediate compound contains two kinds of compounds that can react with both the functional group in formula I and the functional group in formula II. Functional groups, the copolymer of formula I is grafted onto the siloxane of formula II by means of intermediate compounds, and the reactions involved are well known to those skilled in the art.
  • R in Formula II when R in Formula I is COOH, R in Formula II is selected from C1-C6 alkylamino, C1-C6 alkylcarboxy, C1-C6 alkylhydroxy, C1-C6 alkyl At least one of an epoxy group and a C1-C6 alkyl mercapto group.
  • R 6 and R 7 can be grafted by generating an amide bond, anhydride or ester bond through methods known in the art.
  • R in Formula II when R in Formula I is OH, R in Formula II is selected from C1-C6 alkylcarboxy, C1-C6 alkylhydroxy, C1-C6 alkylepoxy, and C1- At least one of the C6 alkyl mercapto groups, in this case, R 6 and R 7 can be grafted by forming an ester bond, condensing or ring-opening by methods known in the art.
  • R 7 in Formula II is selected from C1-C6 alkyl azide.
  • R 6 and R 7 can be selected from the group known in the art. The method produces cycloaddition reaction and grafting.
  • R 6 in Formula I when R 6 in Formula I is carbonyloxy C1-C6 alkylhydroxy, R 7 in Formula II is selected from C1-C6 alkylcarboxy, C1-C6 alkylhydroxy, C1-C6 At least one of an alkyl epoxy group and a C1-C6 alkyl mercapto group.
  • R 6 and R 7 can be grafted by forming an ester bond, condensing or ring-opening by methods known in the art.
  • R7 in the siloxane of Formula II may be a C1-C6 alkenyl group or a C1-C6 alkynyl group.
  • grafting can be achieved by introducing an intermediate compound.
  • the intermediate compound may be a small molecule compound (eg, a relative molecular weight of less than 500) or a polymer (eg, a number average molecular weight of greater than 1000 to less than 10,000).
  • a small molecule compound eg, a relative molecular weight of less than 500
  • a polymer eg, a number average molecular weight of greater than 1000 to less than 10,000.
  • R 6 in formula I is OH or carbonyloxy C1-C6 alkyl hydroxyl group
  • R 7 in formula II is C1-C6 alkylamino group
  • the hydroxyl group on R 6 can first be React with the halogenated C1-C6 alkyl epoxy group of the intermediate compound under alkaline conditions, so that the side chain of the copolymer is first grafted with the epoxy-containing functional group, and then the epoxy functional group is combined with the amino group of R 7 react to achieve grafting.
  • halo C1-C6 alkyl epoxy refers to a halo C1-C6 alkyl group having one epoxy group.
  • the haloC1-C6 alkylepoxy group is epichlorohydrin.
  • the copolymer of Formula I contains at least two, optionally three, of the following polymerized units:
  • n can have the values of x, y and z as described above.
  • the copolymer of Formula I is a terpolymer formed by the copolymerization of three monomers, wherein the first monomer is lithium (meth)acrylate, sodium (meth)acrylate or acrylonitrile; The second monomer is C1-C6 alkyl (meth)acrylate, (meth)acrylamide or acrylonitrile; the third monomer is hydroxy C1-C6 alkyl (meth)acrylate.
  • copolymer of formula I can be formed by copolymerization in random, block, alternating or grafting manners.
  • This application copolymerizes two or more polymer monomers through random, block, alternating, grafting, etc. methods to form a multi-component copolymer.
  • the multi-component copolymer can obtain ideal mechanical properties by regulating the types and proportions of monomers. , chemical and electrochemical properties to meet the requirements of pole piece production.
  • the copolymer of Formula I is a terpolymer formed by the copolymerization of three monomers, wherein the first monomer is lithium (meth)acrylate, sodium (meth)acrylate or acrylonitrile;
  • the second monomer is C1-C6 alkyl (meth)acrylate, (meth)acrylamide or acrylonitrile;
  • the third monomer is hydroxy C1-C6 alkyl (meth)acrylate, wherein the first monomer , the molar ratio of the second monomer and the third monomer is (0.5-3): (0.5-2):1, optionally (0.8-2.5): (0.6-1.5):1, also optionally ( 1.3-2.0):(0.6-1):1.
  • the second aspect of the application provides a method for preparing the adhesive described in the first aspect of the application, wherein the method includes the following steps:
  • Step (1) react the copolymer of formula I with a halogenated C1-C6 alkyl epoxy compound in the presence of a base, and the reaction is performed in the presence of a solvent;
  • Step (2) After optionally removing the solvent and adding water, add the siloxane of formula II (for example, wherein R 7 is C1-C6 alkylamino; R 8 and R 9 are C1-C6 alkyl Oxygen group; R 10 is C1-C6 alkyl) and optionally surfactant and stir.
  • siloxane of formula II for example, wherein R 7 is C1-C6 alkylamino; R 8 and R 9 are C1-C6 alkyl Oxygen group; R 10 is C1-C6 alkyl
  • the weight ratio of the copolymer of Formula I to the halogenated C1-C6 alkyl epoxy compound is 1:(0.005-0.1), optionally 1:(0.008-0.05), or optionally 1:(0.008-0.05). Select 1:(0.01-0.03), and further select 1:(0.01-0.02).
  • the reactions in steps (1) and (2) are performed under an atmosphere of inert gas (such as nitrogen or argon).
  • inert gas such as nitrogen or argon
  • step (1) the reaction is performed at 10°C to 50°C, optionally 20°C to 40°C.
  • step (1) the copolymer of Formula I can be reacted with a base for 1 to 5 hours, and then the halogenated C1-C6 alkyl epoxy compound is added.
  • the halo C1-C6 alkyl epoxy compound is epichlorohydrin.
  • the solvent is selected from at least one of toluene, dichloromethane, chloroform, acetone, and N,N'-dimethylformamide.
  • the base is selected from at least one of sodium hydride and sodium hydroxide, optionally sodium hydride.
  • the molar ratio of the halogenated C1-C6 alkyl epoxy compound to the base is 1:(0.5-2), optionally 1:(0.8-1.5), or optionally 1:(0.9-1.2)1.
  • step (2) after adding the silicone of formula II and optionally the surfactant, the resulting mixture is heated at 30°C to 60°C, optionally 35°C to 55°C. Stir, the stirring time is 10 hours to 50 hours, optional 11 hours to 30 hours.
  • the molar ratio of the halogenated C1-C6 alkyl epoxy compound to the siloxane of Formula II is 1:(0.5-2), optionally 1:(0.8-1.5), and also The optional value is 1: (0.9-1.2).
  • the weight ratio of the copolymer of Formula I to the water is 1:(0.5-6), optionally 1:(1-5), and optionally 1:(1.5-4 ), and optionally 1:(2-3).
  • the weight ratio of water to surfactant is 1:(0.05-0.5), optionally 1:(0.06-0.3), and optionally 1:(0.08-0.2).
  • the water used is deionized water.
  • the viscosity of the adhesive ranges from 100 mPa ⁇ s to 20000 mPa ⁇ s, optionally from 500 mPa ⁇ s to 2000 mPa ⁇ s.
  • the viscosity of the binder can be tested at 25°C using the rotation method according to the standard GB/T 10247-2008.
  • the specific operation of this standard is as follows: fill the beaker or sample container with the sample to be tested, making sure not to introduce air bubbles, and if necessary, vacuum to eliminate the air bubbles. If the sample is volatile or easily hygroscopic, the beaker or sample container must be sealed during the constant temperature process. Place the prepared sample beaker or sample container into the constant temperature bath and ensure sufficient time to reach the specified temperature. Choose a suitable rotor so that the reading is between 20% and 90% of the maximum range.
  • the 63# rotor For the 63# rotor, it should meet the requirements of 1000mpa ⁇ s ⁇ viscosity ⁇ 10000mpa ⁇ s, 20% ⁇ torque percentage ⁇ 90%. If the viscosity result is NG, use the 64# rotor, and the following results should be met at the same time: 10000mpa ⁇ s ⁇ viscosity, 20 % ⁇ torque percentage ⁇ 90%.
  • the rotor groove was flush with the liquid level. Turn on the motor. After 5 minutes, when the viscosity reading of the instrument stabilizes, stop the motor. After the rotor stops, turn on the motor again for the second test until the deviation of the two consecutive test data from the average value is no more than 3%. The result is the sum of the two measured values. average.
  • testing may include the following steps:
  • the aqueous emulsion contains 40% to 90%, optionally 50% to 80%, and optionally 60% to 75% water by weight.
  • the binder of the present application uses deionized water as the solvent, which avoids environmental pollution caused by the use of organic solvents.
  • using deionized water as a solvent can also greatly reduce the production cost of pole pieces.
  • the binder is in the form of an aqueous emulsion with a solid content of 10% to 60%, optionally 20% to 55%, optionally 25% to 45%, and further optionally is 28% to 36%.
  • the solid content of the binder can be tested according to the following method:
  • the aqueous emulsion contains 0.5% to 10%, 1 to 9%, optionally 3% to 8% by weight of surfactant, based on the total weight of the aqueous emulsion.
  • the surfactant is selected from at least one selected from sodium dodecyl sulfonate, tristyryl phosphate, sulfate ester, fatty alcohol polyethylene glycol ether and sodium alkyl succinate sulfonate.
  • the terpolymer is selected from the group consisting of poly(lithium acrylate-methyl acrylate-hydroxymethyl acrylate), poly(lithium acrylate-propyl acrylate-hydroxymethyl acrylate), poly(lithium acrylate-acrylic acid Amyl ester-hydroxymethyl acrylate), poly(lithium acrylate-acrylamide-hydroxymethyl acrylate), poly(acrylonitrile-methyl acrylate-hydroxymethyl acrylate) and poly(sodium acrylate-acrylonitrile-hydroxymethyl acrylate) ) at least one of the following.
  • the siloxane of Formula II is selected from at least one siloxane containing amino groups, carboxyl groups and epoxy groups, optionally selected from trimethoxysilane, triethoxysilane containing amino groups. At least one of silane and tripropoxysilane.
  • the siloxane of Formula II is selected from at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltripropoxysilane. A sort of.
  • the graft polymer is selected from at least one of:
  • x is an integer from 0 to 5000; optionally an integer from 500 to 1500;
  • y is an integer from 0 to 5000; optionally an integer from 500 to 1500;
  • z is an integer from 200 to 3000, optionally an integer from 300 to 1500, and an optional integer from 225 to 1050; further optionally an integer from 525 to 750;
  • a is an integer from 200 to 800; optionally, it is an integer from 500 to 700;
  • a/z is 0.80 to 0.99, optionally 0.85 to 0.98.
  • a schematic diagram of the cross-linked structure formed after hydrolysis and dehydration of the graft polymer during use As an example, a schematic diagram of the cross-linked structure formed after hydrolysis and dehydration of the graft polymer during use.
  • siloxanes There are multiple siloxanes grafted on the main chain of the copolymer.
  • the alkyl groups in the siloxane can be hydrolyzed under acidic, alkaline and other conditions to form silicone hydroxyl groups.
  • the multiple hydroxyl groups connected to the grafted silicon can interact with each other. Hydrogen bonding interactions occur between the adhesives, causing micro-crosslinking between the polymer molecular weights of the adhesive.
  • the two adjacent silanol groups are dehydrated during drying to form a Si-O-Si covalent bond to produce a strong irreversible cross-linked network and improve the internal content of the active material in the pole piece. Concentrate energy to enhance the bonding force between the active material and the conductive agent.
  • the third aspect of the present application provides a slurry, which contains the adhesive described in the first aspect of the present application or the adhesive prepared according to the method described in the second aspect of the present application.
  • the slurry contains 0.5% to 10%, optionally 1% to 5%, by weight of the binder, based on the total weight of the slurry.
  • the slurry is a cathode slurry, which contains 0.5% to 10%, optionally 1% to 5%, of the binder of the present application based on 100 parts by weight of deionized water; 80% to 99%, optional 85% to 98% positive active material; 0.5% to 5%, optional 1% to 3% conductive agent; 0% to 5%, optional 0.5% to 2% stabilizer.
  • the slurry is a negative electrode slurry, which contains 0.5% to 10%, optionally 1% to 5%, of the binder of the present application based on 100 parts by weight of deionized water; 92% to 98%, 95% to 97% negative active material can be selected; 0.5% to 5%, 1% to 2% conductive agent can be selected; 0.1% to 5%, 0.5% to 2% stabilizer can be selected.
  • the stabilizer is selected from soluble polysaccharides and their derivatives, such as methylcellulose and its salts, xanthan gum and its salts, chitosan and its salts, alginic acid and Its salts.
  • soluble polysaccharides and their derivatives such as methylcellulose and its salts, xanthan gum and its salts, chitosan and its salts, alginic acid and Its salts.
  • the positive electrode sheet usually includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon.
  • At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the positive electrode film layer further includes the binder of the present application.
  • the content of the binder in the positive electrode film layer is 0.1% to 5% by mass, optionally 0.5% to 2% by mass.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the above-mentioned components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder of the present application and any other components are dispersed in a solvent (such as N-methylpyrrolidone), a positive electrode slurry is formed; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, where the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative electrode film layer further includes the binder of the present application.
  • the content of the binder in the negative electrode film layer is 0.1% to 5% by mass, optionally 0.5% to 2% by mass.
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as stabilizers (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • auxiliaries such as stabilizers (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components for preparing the negative electrode sheet, such as the negative active material, the conductive agent, the binder of the present application and any other components are dispersed in a solvent (for example, in deionized water), a negative electrode slurry is formed; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent For example, in deionized water
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the type of electrolyte in this application can be selected according to needs.
  • the electrolyte can be liquid, gel, or completely solid.
  • the electrolyte is liquid and includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte optionally also includes additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the secondary battery further includes a separator film.
  • a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 1 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • FIG. 6 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the tensile performance test of the film refers to the national standard GB/T 1040-1992.
  • the binder of the present invention is dried, and after the obtained adhesive film is completely dry, it is cut into an object with a specific shape weighing about 0.5g and soaked in an electrolyte (the same as the electrolyte used in the secondary battery below). , seal and place in an ambient temperature of 70°C. Take out and dry the surface electrolyte every 7 days, weigh and record.
  • an electrolyte the same as the electrolyte used in the secondary battery below.
  • the end of the steel plate that is not attached to the pole piece is fixed with the lower clamp. Fold the paper tape upward and fix it with the upper clamp.
  • the axis direction of the pole piece is consistent with the direction of force application.
  • CRM-01 pole piece resistance tester to test the resistance of the positive electrode diaphragm. Each group was tested 5 times and the average value was taken.
  • the secondary battery prepared as follows at a constant current of 1/3C to 3.65V, then charge at a constant voltage of 3.65V to a current of 0.05C, leave it aside for 5 minutes, and then discharge it at a constant current of 1/3C to 2.7V. , the obtained capacity is recorded as the initial capacity C 0 .
  • the battery capacity retention rate after each cycle P n C n /C 0 *100%.
  • the battery capacity retention rate data corresponding to Example 13 in Table 2 is the data measured after 800 cycles under the above test conditions, that is, the value of P800.
  • the obtained poly(lithium acrylate-methyl acrylate-hydroxymethyl acrylate) with epoxy groups was added to 500 ml of deionized water after rotary evaporation and drying, and 59.5g (0.219mol) dodecane was added.
  • sodium sulfonate add 3.92g (0.0219mol) 3-aminopropyltrimethoxysilane, and stir at 50°C for 24h.
  • a siloxane-functionalized poly(lithium acrylate-methyl acrylate-hydroxymethyl acrylate) aqueous adhesive emulsion was obtained, with a viscosity of 1500 mPa ⁇ s and a solid content of 34.7%. See Figure 7 for the infrared spectrum.
  • the preparation method is basically the same as in Example 1, except that 1.06g of sodium hydride, 4.06g of epichlorohydrin, and 7.84g of 3-aminopropyltrimethoxysilane are added.
  • the preparation method is basically the same as in Example 1, except that 1.59g of sodium hydride, 6.09g of epichlorohydrin, and 11.76g of 3-aminopropyltrimethoxysilane are added.
  • the preparation method is basically the same as in Example 1, except that the copolymer used is poly(lithium acrylate-propyl acrylate-hydroxymethyl acrylate) with a number average molecular weight of 200,000.
  • the preparation method is basically the same as in Example 1, except that the copolymer used is poly(lithium acrylate-pentyl acrylate-hydroxymethyl acrylate) with a number average molecular weight of 200,000.
  • the preparation method is basically the same as in Example 1, except that the copolymer used is poly(lithium acrylate-acrylamide-hydroxymethyl acrylate) with a number average molecular weight of 200,000.
  • the preparation method is basically the same as that in Example 1, except that the copolymer used is poly(acrylonitrile-methyl acrylate-hydroxymethyl acrylate) with a number average molecular weight of 200,000.
  • the preparation method is basically the same as that in Example 1, except that the copolymer used is poly(sodium acrylate-acrylonitrile-hydroxymethyl acrylate) with a number average molecular weight of 200,000.
  • the preparation method is basically the same as in Example 1, except that the siloxane compound used is 3-aminopropyltriethoxysilane (0.0219 mol).
  • the preparation method is basically the same as that in Example 1, except that the siloxane compound used is 3-aminopropyltripropoxysilane (0.0219 mol).
  • the preparation method is basically the same as that in Example 1, except that 3-aminopropyltripropoxysilane is not used for grafting.
  • Preparation of the positive electrode sheet Add 95 parts by weight of lithium iron phosphate, 2 parts by weight of conductive carbon black Super P, and 1 part by weight of carboxymethyl cellulose into the mixing tank, add 30 parts by weight of deionized water, and knead for 1 hour, and continue Add 70 parts by weight of deionized water and stir for 1.5 hours, then add 2 parts by weight of the aqueous adhesive emulsion synthesized in Example 1, and continue stirring for 1 hour to obtain a water-based positive electrode slurry.
  • the obtained slurry was coated on the surface of aluminum foil (thickness 12 ⁇ m) by extrusion coating, and dried at 120°C for 5 minutes to obtain a water-based positive electrode sheet.
  • Preparation of the negative electrode sheet Combine the negative active material artificial graphite, the conductive agent acetylene black, the binder styrene-butadiene rubber (SBR), and the thickener sodium carboxymethyl cellulose (CMC-Na) in a weight ratio of 95:1: 3:1 was dissolved in deionized water, stirred thoroughly and mixed evenly to prepare a negative electrode slurry; the negative electrode slurry was coated on the negative electrode current collector copper foil, and then dried, cold pressed, and cut to obtain negative electrode pieces.
  • SBR binder styrene-butadiene rubber
  • CMC-Na thickener sodium carboxymethyl cellulose
  • Isolation film Polypropylene film is used.
  • Preparation of secondary batteries stack and wind the above-mentioned positive electrode sheets, separators, and negative electrode sheets in order to obtain an electrode assembly; put the electrode assembly into the outer packaging, add the electrolyte prepared above, package and let it stand , formation, aging and other processes, a secondary battery is obtained.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 2.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 3.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 4.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 5.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 6.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 7.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 8.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 9.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 10.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 11.
  • the preparation method is basically the same as that in Example 13, except that when preparing the positive electrode piece, the adhesive used is the adhesive synthesized in Example 12.

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Abstract

本申请涉及一种粘结剂、包含所述粘结剂的浆料及其相关的电极极片、二次电池、电池模块、电池包和用电装置。本申请的粘结剂具有较好的粘结性能、溶胀率低、内聚力高且所制备的极片在烘干过程中不易出现开裂、卷边等问题。

Description

粘结剂及其应用 技术领域
本申请涉及二次电池的技术领域，尤其涉及一种粘结剂、包含所述粘结剂的浆料及其相关的电极极片、二次电池、电池模块、电池包和用电装置。
背景技术
近年来，二次电池的应用范围越来越广泛，例如，可应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。随着二次电池的广泛应用，人们对电池性能的要求也越来越高。
然而，现有技术中用于制备电池极片的粘接剂的粘接力不足、内聚力低、所形成的胶膜的溶胀比高，使极片在烘干过程中容易出现开裂、卷边以及所得极片脆性差等问题，这些都严重影响了二次电池的电性能。
因此，仍需对制备电极极片所使用的粘结剂作出改进，以获得电性能更好的二次电池。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种粘结剂、包含所述粘结剂的浆料及其相关的电极极片、二次电池、电池模块、电池包和用电装置，旨在改善使用现有技术的粘结剂所出现的问题，从而改善二次电池的电性能。
为达到上述目的，本申请第一方面提供了一种粘结剂，其包含接枝聚合物，所述接枝聚合物包含作为主链的式I的共聚物以及接枝在主链上的式II的硅氧烷：
Figure PCTCN2022101486-appb-000001
其中R 1、R 2和R 3各自独立地选自氢和C1-C6烷基中的至少一个，可选地各自独立地选自氢和甲基中的至少一个；
R 4选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)OLi、C(＝O)ONa和CN中的至少一个；
R 5选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个；
R 6选自COOH、OH、CN和羰基氧基C1-C6烷基羟基中的至少一个，可选地选自OH和羰基氧基C1-C6烷基羟基中的至少一个；
其中x、y各自独立地为0至5000的整数，可选为500至1500的整数；x和y不同时为0；
z为100至3000的整数，可选为200至1500的整数；
Figure PCTCN2022101486-appb-000002
其中R 7选自C1-C6烯基、C1-C6炔基、C1-C6烷基叠氮基、C1-C6烷基氨基、C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，可选地选自C1-C6烷基氨基、C1-C6烷基羧基和C1-C6烷基环氧基中的至少一个；
R 8和R 9各自独立地选自C1-C6烷基和C1-C6烷基氧基中的至少一个；
R 10为C1-C6烷基。
在任意实施方式中，所述式I的共聚物在所述接枝聚合物中的重量百分比为90％至99.9％。
在任意实施方式中，所述式II的硅氧烷在所述接枝聚合物中的接枝比例为0.1％至5％。
在任意实施方式中，所述式I的共聚物为由三种单体共聚形成的三元共聚物，其中第一单体为(甲基)丙烯酸锂、(甲基)丙烯酸钠或丙烯腈；第二单体为(甲基)丙烯酸C1-C6烷基酯、(甲基)丙烯酰胺或丙烯腈；第三单体为(甲基)丙烯酸羟基C1-C6烷基酯。
在任意实施方式中，第一单体、第二单体和第三单体的摩尔比为(0.5-3)：(0.5-2)：1，可选为(0.8-2.5)：(0.6-1.5)：1。
在任意实施方式中，所述三元共聚物选自聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酸丙酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酸戊酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酰胺-丙烯酸羟甲酯)、聚(丙烯睛-丙烯酸甲酯-丙烯酸羟甲酯)和聚(丙烯酸钠-丙烯睛-丙烯酸羟甲酯)中的至少一种。
在任意实施方式中，所述式II的硅氧烷选自3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷和3-氨丙基三丙氧基硅烷中的至少一种。
在任意实施方式中，所述粘结剂为水乳液的形式，其中所述接枝聚合物在水乳液中的重量百分比为5％至50％，可选10％至40％。
在任意实施方式中，所述粘结剂的粘度为100mPa·s至20000mPa·s，可选为500mPa·s至2000mPa·s。
本申请第二方面提供了一种制备本申请第一方面所述的粘结剂的方法，其中所述方法包含以下步骤：
步骤(1)：将式I的共聚物与卤代C1-C6烷基环氧基化合物在碱的存在下进行反应，所述反应在溶剂的存在下进行；
步骤(2)：在任选地除去溶剂后并加入水，然后再加入式II的硅氧烷和任选地表面活性剂并进行搅拌。
在任意实施方式中，所述式I的共聚物与卤代C1-C6烷基环氧 基化合物的重量比为1:(0.005-0.1)，可选为1:(0.01-0.05)。
在任意实施方式中，所述卤代C1-C6烷基环氧基化合物与式II的硅氧烷的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)。
在任意实施方式中，所述卤代C1-C6烷基环氧基化合物为环氧氯丙烷；
在任意实施方式中，所述碱选自氢化钠和氢氧化钠中的至少一种，可选为氢化钠；
在任意实施方式中，所述卤代C1-C6烷基环氧基化合物与所述碱的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)1。
本申请第三方面提供了一种浆料，其包含本申请第一方面所述的粘结剂或根据本申请第二方面所述的方法制备的粘结剂。
在任意实施方式中，所述浆料包含重量百分比为0.5％至5％的所述粘结剂。
本申请第四方面提供了一种电极极片，其包含集流体和设置在集流体至少一个表面的由本申请第三方面所述的浆料形成的膜层。
本申请第五方面提供了一种二次电池，其包含本申请第四方面所述的电极极片。
本申请的第六方面提供一种电池模块，包括本申请的第五方面的二次电池。
本申请的第七方面提供一种电池包，包括本申请的第六方面的电池模块。
本申请的第八方面提供一种用电装置，包括选自本申请的第五方面的二次电池、本申请的第六方面的电池模块或本申请的第七方面的电池包中的至少一种。
本申请的粘结剂具有较好的粘结性能、内聚力高、所形成的胶膜的溶胀率低并且由其所制备的极片在烘干过程中不易出现开裂、卷边等问题，所制备的二次电池也具有较好的容量保持率。
附图说明
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
图7是本申请实施例1的接枝聚合物的红外谱图，其中特征峰1087cm -1表明共聚物接枝上了硅氧烷化合物。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的粘结剂、包含所述粘结剂的浆料及其相关的电极极片、二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也 是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
如果没有特别的说明，在本申请中，所有操作均在常温(25℃)和常压(101kPa)下进行。
发明人在研究中发现，在使用现有技术中的粘结剂，特别是聚(甲基)丙烯酸类水系粘接剂时，由其制备的正极极片存在脆性高、柔韧性差、内聚力低、在电解液中溶胀系数高等问题。然而，发明人出乎意料发现，在聚(甲基)丙烯酸类聚合物上接枝含有硅氧烷的化合物后，所得粘结剂可以明显改善上述问题。这种改善对于要求厚涂布以及高压实密度的使用情况是特别有利的。
不囿于任何理论，发明人认为，当将本申请的粘接剂用于水系浆料制备，在浆料涂覆于集流体并烘干的过程中，由于浆料中的溶剂在 烘干的过程中被带走，导致粘结剂浓度逐渐增大，各个主链上接枝的硅氧烷水解形成的硅羟基浓度增大，硅羟基之间接触概率增大。相邻的两个硅羟基在烘干中脱水，形成Si-O-Si共价键，产生较强的不可逆交联网路，提高了极片中活性物质的内聚能，增强活性物质和导电剂之间的粘接力。同时，在浆料与集流体接触的界面上，粘接剂中的硅羟基可以与集流体中的羟基在烘干脱水过程中形成Si-O-R共价键，提高了活性物质与集流体的粘接强度。
此外，由于主链上接枝有硅氧烷，其能够在酸性、碱性等条件下水解形成硅羟基，各个分子链的硅羟基之间形成弱的氢键相互作用，使粘接剂在浆料中产生可逆交联。这种可逆交联能够在正负极浆料静置过程中使浆料凝胶化，阻止其内部不同组分由于密度不同而产生上浮或沉降，提高浆料的稳定性、均一性，延长浆料的保存时间。同时，由于粘接剂在浆料中负载量较低，同时浆料中含有大量溶剂，这使得本身较弱的氢键相互作用只能产生极低的相互作用力，在外界极小的剪切力作用下氢键相互作用即可被破坏，导致可逆交联断裂，浆料恢复原有的流动性和流变性能，而使得浆料具有较好的可加工性能。
为此，本申请第一方面提供了一种粘结剂，其包含接枝聚合物，所述接枝聚合物包含作为主链的式I的共聚物以及接枝在主链上的式II的硅氧烷：
Figure PCTCN2022101486-appb-000003
其中R 1、R 2和R 3各自独立地选自氢和C1-C6烷基中的至少一个，可选地各自独立地选自氢和甲基中的至少一个；
R 4选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)OLi、C(＝O)ONa和CN中的至少一个；
R 5选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个；
R 6选自COOH、OH、CN和羰基氧基C1-C6烷基羟基中的至少一个，可选地选自OH和羰基氧基C1-C6烷基羟基中的至少一个；
其中x、y各自独立地为0至5000的整数，可选为100至4000的整数，还可选为200至3000的整数，还进一步可选为500至1500的整数；x和y不同时为0；
z为100至3000的整数，可选为150至2500的整数，还可选为180至2000的整数，还进一步可选为200至1500的整数；
Figure PCTCN2022101486-appb-000004
其中R 7选自C1-C6烯基、C1-C6炔基、C1-C6烷基叠氮基、C1-C6烷基氨基、C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，可选地选自C1-C6烷基氨基、C1-C6烷基羧基和C1-C6烷基环氧基中的至少一个；
R 8和R 9各自独立地选自C1-C6烷基和C1-C6烷基氧基中的至少一个；
R 10为C1-C6烷基。
在本申请中，应理解，“C1-C6烷基”是指具有1至6个碳原子的直链烃或支链烃，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,2-二甲基丙基、1,3-二甲基丁基、1,4-二甲基丁基、2,3-二甲基丁基、1,1-二甲基丁基、2,2-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基和2-乙基丁基。还可选具有1至4个碳原子的烷基，例如尤其是甲基、乙基、正 丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
在一些实施方式中，所述接枝聚合物的数均分子量为50,000至1,000,000，可选为100,000至800,000，还可选为150,000至600,000。
在一些实施方式中，所述式I的共聚物在所述接枝聚合物中的重量百分比为90％至99.9％，还可选为90.5％至98.5％，进一步可选为91％至98％，基于所述接枝聚合物的总重量计。
在一些实施方式中，所述接枝聚合物中式II的硅氧烷的重量百分比为0.1％至10％，可选为0.5％至8％，还可选为1％至6％，基于所述接枝聚合物的总重量计。
在一些实施方式中，所述式I的共聚物的数均分子量为20,000至500,000，可选为50,000至400,000，还可选为100,000至350,000。
在一些实施方式中，所述式II的硅氧烷的相对分子量为50至500，可选为100至400，还可选为150至350。
在本申请中，数均分子量通过凝胶渗透色谱(GPC)法，按照GB/T 21863-2008《凝胶渗透色谱法(GPC)用四氢呋喃做淋洗液》测定。
在一些实施方式中，所述式II的硅氧烷在所述接枝聚合物中的接枝比例为0.1至5％，可选为0.5至3.5％，还可选为0.8％至3％。在本申请中，表述“接枝比例”应理解为，在所述接枝聚合物中，被接枝的共聚单体的摩尔量与全部共聚单体的摩尔量之比。例如，在制备接枝聚合物时，所使用的作为主链的式I的共聚物由共计10摩尔的共聚单体聚合而成，而在后续仅使用0.1摩尔的式II的硅氧烷进行接枝，则可以理解，这里的接枝比例为0.1/10*100％＝1％。
在本申请中，应理解，所述式I的共聚物与式II的硅氧烷之间的反应可以直接进行，例如式I的共聚物支链上含有可与式II的硅氧烷上的烯基、炔基、叠氮基、氨基、羧基、羟基、环氧基团或巯基直接反应的基团；当式I的共聚物上无法与式II的硅氧烷化合物直接反应 的情况下，式I的共聚物可以先与中间体化合物反应，然后再与式II的硅氧烷反应，其中所述中间体化合物含有可与式I中的官能团和式II中的官能团两者反应的两种官能团，借助于中间体化合物使式I的共聚物接枝上式II的硅氧烷，其中所涉及的反应为本领域技术人员所公知的。
在一些实施方式中，当式I中的R 6为COOH时，式II中的R 7选自C1-C6烷基氨基、C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，在这种情况下，R 6与R 7可通过本领域公知的方法来生成酰胺键、酸酐或酯键而进行接枝。
在一些实施方式中，当式I中的R 6为OH时，式II中的R 7选自C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，在这种情况下，R 6与R 7可通过本领域公知的方法来生成酯键、发生缩合或开环而进行接枝。
在一些实施方式中，当式I中的R 6为CN时，式II中的R 7选自C1-C6烷基叠氮基，在这种情况下，R 6与R 7可通过本领域公知的方法发生环加成反应而进行接枝。
在一些实施方式中，当式I中的R 6为羰基氧基C1-C6烷基羟基时，式II中的R 7选自C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，在这种情况下，R 6与R 7可通过本领域公知的方法来生成酯键、发生缩合或开环而进行接枝。
在一些实施方案中，当式I的共聚物中包含有可反应的不饱和键时，式II的硅氧烷中的R 7可为C1-C6烯基或C1-C6炔基。
在一些实施方案中，当R 6与R 7之间无法直接进行反应时，其可以通过引入中间体化合物来实现接枝。
在一些实施方式中，所述中间体化合物可为小分子化合物(例如相对分子量小于500)或聚合物(例如数均分子量大于1000至小于10,000)。对于中间体化合物的具体种类，本领域的技术人员可根据式I的共聚物中所包含的反应性基团与式II的硅氧烷中的R 7来具体选择。
在一些实施方式中，当式I中的R 6为OH或羰基氧基C1-C6烷基羟基，式II中的R 7为C1-C6烷基氨基时，可以首先将R 6上的羟基在碱性条件下与中间体化合物卤代C1-C6烷基环氧基进行反应，使共聚物的侧链上首先接枝含环氧基的官能团，然后再将环氧基官能团与R 7的氨基进行反应，从而实现接枝。
在本申请中，术语“卤代C1-C6烷基环氧基”是指具有一个环氧基的卤代C1-C6烷基。
在一些实施方式中，所述卤代C1-C6烷基环氧基为环氧氯丙烷。
在一些实施方式中，所述式I的共聚物包含以下至少两种，可选三种聚合单元：
Figure PCTCN2022101486-appb-000005
其中m为0至50的整数，可选1至5的整数；n可具有上文所述的x、y和z的值。
在一些实施方式中，所述式I的共聚物为由三种单体共聚形成的三元共聚物，其中第一单体为(甲基)丙烯酸锂、(甲基)丙烯酸钠或丙烯腈；第二单体为(甲基)丙烯酸C1-C6烷基酯、(甲基)丙烯酰胺或丙烯腈；第三单体为(甲基)丙烯酸羟基C1-C6烷基酯。
在本申请中，应理解，式I的共聚物中的聚合单元
Figure PCTCN2022101486-appb-000006
Figure PCTCN2022101486-appb-000007
可以通过无规、嵌段、交替或接枝等方式进行共聚而形成式I的共聚物。
本申请将两种或多种聚合物单体通过无规、嵌段、交替、接枝等方式共聚而形成多元共聚物，该多元共聚物可通过调控的单体种类与比例而获得理想的力学、化学、电化学性能，从而满足极片生产的要求。
在一些实施方式中，所述式I的共聚物为由三种单体共聚形成的三元共聚物，其中第一单体为(甲基)丙烯酸锂、(甲基)丙烯酸钠或丙烯腈；第二单体为(甲基)丙烯酸C1-C6烷基酯、(甲基)丙烯酰胺或丙烯腈；第三单体为(甲基)丙烯酸羟基C1-C6烷基酯，其中第一单体、第二单体和第三单体的摩尔比为(0.5-3):(0.5-2):1，可选为(0.8-2.5):(0.6-1.5):1，还可选为(1.3-2.0):(0.6-1):1。
本申请第二方面提供了一种制备本申请第一方面所述的粘结剂的方法，其中所述方法包含以下步骤：
步骤(1)：将式I的共聚物与卤代C1-C6烷基环氧基化合物在碱的存在下进行反应，所述反应在溶剂的存在下进行；
步骤(2)：在任选地除去溶剂后并加入水，然后再加入式II的硅氧烷(例如，其中R 7为C1-C6烷基氨基；R 8和R 9为C1-C6烷基氧基；R 10为C1-C6烷基)和任选地表面活性剂并进行搅拌。
在一些实施方式中，所述式I的共聚物与卤代C1-C6烷基环氧基化合物的重量比为1:(0.005-0.1)，可选为1:(0.008-0.05)，还可选为1:(0.01-0.03)，还进一步可选为1:(0.01-0.02)。
在一些实施方式中，在步骤(1)和(2)中的反应在惰性气体(例如氮气或氩气)气氛下进行。
在一些实施方式中，在步骤(1)中，反应在10℃至50℃，可选为20℃至40℃下进行。
在一些实施方式中，在步骤(1)中，可将式I的共聚物先与碱反应1-5小时，然后再加入卤代C1-C6烷基环氧基化合物。
在一些实施方式中，所述卤代C1-C6烷基环氧基化合物为环氧氯丙烷。
在一些实施方式中，所述溶剂选自甲苯、二氯甲烷、三氯甲烷、丙酮和N,N’-二甲基甲酰胺中的至少一种。
在一些实施方式中，所述碱选自氢化钠和氢氧化钠中的至少一种，可选为氢化钠。
在一些实施方式中，所述卤代C1-C6烷基环氧基化合物与所述碱的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)1。
在一些实施方式中，在步骤(2)中，在加入式II的硅氧烷和任选地表面活性剂之后，将所得混合物在30℃至60℃，可选为35℃至55℃下进行搅拌，搅拌时间为10小时至50小时，可选为11小时至30小时。
在一些实施方式中，所述卤代C1-C6烷基环氧基化合物与式II的硅氧烷的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)。
在一些实施方式中，所述式I的共聚物与所述水的重量比为1:(0.5-6)，可选为1:(1-5)，还可选为1:(1.5-4)，还可选为1:(2-3)。
在一些实施方式中，所述水与表面活性剂的重量比为1:(0.05-0.5)，可选为1:(0.06-0.3)，还可选为1:(0.08-0.2)。
在一些实施方式中，所述粘结剂为水乳液形式，其中所述接枝聚合物在水乳液中的重量百分比为5％至50％，可选10％至40％，还可选为20％至32％，基于所述水乳液的总重量计。
在本申请中，如无特别说明，所使用的水均为去离子水。
在一些实施方式中，所述粘结剂的粘度为100mPa·s至20000mPa·s，可选为500mPa·s至2000mPa·s。
在本申请中，所述粘结剂的粘度可在25℃下，采用旋转法根据标准GB/T 10247-2008进行测试。该标准具体操作如下：在烧杯或盛样器中装满待测样品，确保不要引入气泡，如有必要，抽真空消除气泡。若样品挥发或易吸湿等，在恒温过程中要密封烧杯或盛样器。将准备好样品的烧杯或盛样器放入恒温浴中，确保时间充分以达到规定 温度。选择合适转子，使读数在最大量程的20％～90％。对63#转子，应满足1000mpa·s≤粘度≤10000mpa·s，20％≤扭矩百分比≤90％，若粘度结果NG，改用64#转子，应同时满足如下结果：10000mpa·s＜粘度，20％≤扭矩百分比≤90％。测试过程中转子凹槽与液面平齐。开启电机，5min后仪器粘度读数稳定后，停止电机，等转子停止后再次开启电机进行第二次测试，直到连续两次测试数据相对平均值的偏差不大于3％，结果取两次测定值的平均数。
本文中，所述测试可包括以下步骤：
使用旋转粘度计，根据样品粘度选择转子。使用粘度计升降架，使粘度计缓慢下降，控制转子浸没在液体中，直至转子上的标记与液面持平。测试温度：25℃，转速：12rpm。按测量键开始测量，5min后数据保持稳定后，读取粘度值即可。
在一些实施方式中，所述水乳液包含重量百分比为40％至90％，可选50％至80％，还可选60％至75％的水。相比于传统浆料中必须使用有机溶剂如N-甲基吡咯烷酮，本申请的粘结剂使用去离子水作为溶剂，避免了因使用有机溶剂导致环境污染。同时，使用去离子水作为溶剂也能够极大降低极片生产成本。
在一些实施方式中，所述粘结剂为水乳液的形式，其固含量为10％至60％，可选为20％至55％，还可选为25％至45％，还进一步可选为28％至36％。
所述粘结剂的固含量可根据以下方法进行测试：
取重量M1的粘结剂放入烘箱中，在120℃下放置48h烘干，烘干后重量M2，固含量＝M2/M1×100％。
在一些实施方式中，所述水乳液包含重量百分比为0.5％至10％，1至9％，可选3％至8％的表面活性剂，基于水乳液的总重量计。所述表面活性剂选自十二烷基磺酸钠、三苯乙烯基磷酸酯、硫酸酯、脂肪醇聚乙二醇醚和琥珀酸烷基磺酸钠中的至少一种。
在一些实施方式中，所述三元共聚物选自聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酸丙酯-丙烯酸羟甲 酯)、聚(丙烯酸锂-丙烯酸戊酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酰胺-丙烯酸羟甲酯)、聚(丙烯睛-丙烯酸甲酯-丙烯酸羟甲酯)和聚(丙烯酸钠-丙烯睛-丙烯酸羟甲酯)中的至少一种。
在一些实施方式中，所述式II的硅氧烷选自包含氨基、羧基和环氧基的硅氧烷中的至少一种，可选为选自包含氨基的三甲氧基硅烷、三乙氧基硅烷和三丙氧基硅烷中的至少一种。
在一些实施方式中，所述式II的硅氧烷选自3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷和3-氨丙基三丙氧基硅烷中的至少一种。
在一些实施方式中，所述接枝聚合物选自以下中的至少一个：
Figure PCTCN2022101486-appb-000008
其中x为0至5000的整数；可选为500至1500的整数；
y为0至5000的整数；可选为500至1500的整数；
z为200至3000的整数，可选为300至1500的整数，还可选225至1050的整数；进一步可选为525至750的整数；
a为200至800的整数；可选为500至700的整数；
可选地，a/z为0.80至0.99，可选地为0.85至0.98。
作为示例，以下示出了本申请一个具体的接枝聚合物的合成路线图：
Figure PCTCN2022101486-appb-000009
作为示例，所述接枝聚合物在使用过程中在水解和脱水后形成的交联结构的示意图
Figure PCTCN2022101486-appb-000010
共聚物主链上接枝有多个硅氧烷，该硅氧烷中的烷基能够在酸性、碱性等条件下水解形成硅羟基，其接枝的硅上连接的多个羟基能够互相之间产生氢键相互作用，使粘接剂的聚合物分子量间产生微交联。在后续烘干脱水的情况下，相邻的两个硅羟基在烘干中脱水，形成Si-O-Si共价键，以产生较强的不可逆交联网路，提高极片中活性物质的内聚能，增强活性物质和导电剂之间的粘接力。
本申请第三方面提供了一种浆料，其包含本申请第一方面所述的粘结剂或根据本申请第二方面所述的方法制备的粘结剂。
在一些实施方式中，所述浆料包含重量百分比为0.5％至10％，可选为1％至5％的所述粘结剂，基于浆料的总重量计。
在一些实施方式中，所述浆料为正极浆料，其包含基于100重量份的去离子水计的0.5％至10％，可选1％至5％的本申请的粘结剂；80％至99％，可选85％至98％的正极活性材料；0.5％至5％，可选1％至3％的导电剂；0％至5％，可选0.5％至2％的稳定剂。
在一些实施方式中，所述浆料为负极浆料，其包含基于100重量份的去离子水计的0.5％至10％，可选1％至5％的本申请的粘结剂；92％至98％，可选95％至97％的负极活性材料；0.5％至5％，可选1％ 至2％的导电剂；0.1％至5％，可选0.5％至2％的稳定剂。
在一些实施方式中，所述稳定剂选自可溶性多糖类及其衍生物，如甲基纤维素及其盐类、黄原胶及其盐类、壳聚糖及其盐类、海藻酸及其盐类。关于正极活性材料、负极活性材料以及导电剂将在下文中详述。
[正极极片]
正极极片通常包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，正极膜层包括正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、 LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中，正极膜层还包括本申请的粘结剂。
在一些实施方式中，所述粘结剂正极膜层中的含量为0.1质量％至5质量％，可选0.5质量％至2质量％。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、本申请的粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙 二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还包括本申请的粘结剂。
在一些实施方式中，所述粘结剂负极膜层中的含量为0.1质量％至5质量％，可选0.5质量％至2质量％。
在一些实施方式中，负极膜层还可选地包括导电剂。作为示例，导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如稳定剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、本申请的粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，电解质为液态的，且包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，电解液还可选地包括添加剂。作为示例，添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸 丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提 供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
[实施例]
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
【红外光谱测试】
依据标准GB/T6040-2002红外光谱分析方法，采用美国尼高力(nicolet)公司的IS10型傅里叶变换红外光谱仪。
【胶膜拉伸性能测试】
胶膜拉伸性能测试参照国标GB/T 1040-1992。
【胶膜溶胀性测试】
将本发明的粘结剂进行烘干，待所得胶膜完全干燥后，裁剪为具有特定形状的重约0.5g的物体，浸泡于电解液(与下文二次电池中 使用的电解液相同)中，密封后放于70℃的环境温度中，隔7天取出擦干表面电解液，称重并记录。
【正极片外观测试】
观察制备的正极片的外观，并按照以下标准分类：
如果外观无划痕、凸点等异常现象，则记为优；
如果外观划痕小于等于1处，且不露金属或凸点≤3处，则记为良；
如果外观划痕大于1处或凸点＞3处，则记为差。
【粘接力测试】
即180°剥离强度的测试。取待测试正极极片，极片外观良好，不允许外观坏品。用刀片截取宽30mm*长度为140mm的试样。将专用双面胶NITTO.NO5000NS贴于钢板上，胶带宽度20mm*长度120mm。将上述截取的固定尺寸极片试样贴在双面胶上，测试面朝下，后用3kg压辊沿在极片的表面同一个方向滚压三次。将宽度与极片等宽，长度大于试样长度120mm的纸带插入极片下方，并且用皱纹胶固定。然后将该样品固定在试验机上，钢板未贴极片的一端用下夹具固定，将纸带向上翻折，用上夹具固定，极片轴线方向与施力方向保持一致，试验机以10mm/min剥离速度加载，直至极片断裂，停止测试，记录最大负载力为F(单位N)，极片宽度L＝20mm，根据f1＝F/L，计算剥离强度f1(单位N/m)。
【内聚力测试】
即180°剪切强度测试。取待测试正极极片，极片外观良好，不允许外观坏品。用刀片截取宽30mm*长度为130mm的试样。将专用双面胶NITTO.NO5000NS贴于钢板上，胶带宽度20mm*长度130mm。将上述截取的固定尺寸极片试样贴在双面胶上，测试面朝上，然后将宽度为20mm，长度大于试样长度140mm的低粘绿胶带 MD-XTG-620-2335L平整的粘在测试面表面，后用3kg压辊沿在极片的表面同一个方向滚压三次。然后将该样品固定在试验机上，钢板未贴极片的一端用下夹具固定，将绿胶带向上翻折，用上夹具固定，极片轴线方向与施力方向保持一致，试验机以10mm/min剥离速度加载，直至极片断裂，停止测试，记录最大负载力为F(单位N)，极片宽度L＝20mm，根据f1＝F/L，计算剥离强度f1(单位N/m)。
【正极膜片对折测试】
将正极膜片对折后使用重量为2kg的压辊来回辊压3次，之后将正极膜片铺平，重复上述操作，直至对折处漏光，记录对折次数。每组测试5次，取平均值。
【正极膜片的电阻测试】
使用CRM-01极片电阻测试仪测试正极膜片的电阻。每组测试5次，取平均值。
【电池容量保持率】
在25℃下，将根据下文制备的二次电池，以1/3C恒流充电至3.65V，再以3.65V恒定电压充电至电流为0.05C，搁置5min，再以1/3C放电至2.7V，所得容量记为初始容量C 0。对上述同一个电池重复以上步骤，并同时记录循环第n次后电池的放电容量C n，则每次循环后电池容量保持率P n＝C n/C 0*100％。该测试过程中，第一次循环对应n＝1、第二次循环对应n＝2、……第100次循环对应n＝100。表2中实施例13对应的电池容量保持率数据是在上述测试条件下循环800次之后测得的数据，即P800的值。
实施例1
将200g聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)(购自上海阿拉丁生化科技股份有限公司，其中聚合单体丙烯酸锂：丙烯酸甲酯： 丙烯酸羟甲酯＝5：2：3(摩尔比)，数均分子量为20万)加入烧瓶中，加入500毫升无水甲苯搅拌溶解，加入0.53g(0.0219mol)的氢化钠，在氮气保护条件下室温搅拌4小时，继续向其中加入2.03g(0.0219mol)的环氧氯丙烷，室温搅拌12小时，得到带有环氧基团的聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)。将所得到的带有环氧基团的聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)通过旋转蒸发并烘干后加入到500毫升去离子水中，加入59.5g(0.219mol)十二烷基磺酸钠，加入3.92g(0.0219mol)3-氨丙基三甲氧基硅烷，在50℃下搅拌24h。得到硅氧烷官能化的聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)水系粘接剂乳液，粘度为1500mPa·s，固含量为34.7％，红外光谱参见图7。
实施例2
其制备方法与实施例1基本相同，不同之处在于，使用聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)，其中丙烯酸锂：丙烯酸甲酯：丙烯酸羟甲酯的摩尔比例＝4：3：3。
实施例3
其制备方法与实施例1基本相同，不同之处在于，使用聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)，其中丙烯酸锂：丙烯酸甲酯：丙烯酸羟甲酯的摩尔比例＝3：4：3。
实施例4
其制备方法与实施例1基本相同，不同之处在于，加入1.06g的氢化钠、4.06g的环氧氯丙烷、7.84g的3-氨丙基三甲氧基硅烷。
实施例5
其制备方法与实施例1基本相同，不同之处在于，加入1.59g的氢化钠、6.09g的环氧氯丙烷、11.76g的3-氨丙基三甲氧基硅烷。
实施例6
其制备方法与实施例1基本相同，不同之处在于，使用的共聚物为聚(丙烯酸锂-丙烯酸丙酯-丙烯酸羟甲酯)，数均分子量为20万。
实施例7
其制备方法与实施例1基本相同，不同之处在于，使用的共聚物为聚(丙烯酸锂-丙烯酸戊酯-丙烯酸羟甲酯)，数均分子量为20万。
实施例8
其制备方法与实施例1基本相同，不同之处在于，使用的共聚物为聚(丙烯酸锂-丙烯酰胺-丙烯酸羟甲酯)，数均分子量为20万。
实施例9
其制备方法与实施例1基本相同，不同之处在于，使用的共聚物为聚(丙烯睛-丙烯酸甲酯-丙烯酸羟甲酯)，数均分子量为20万。
实施例10
其制备方法与实施例1基本相同，不同之处在于，使用的共聚物为聚(丙烯酸钠-丙烯睛-丙烯酸羟甲酯)，数均分子量为20万。
实施例11
其制备方法与实施例1基本相同，不同之处在于，使用的硅氧烷化合物为3-氨丙基三乙氧基硅烷(0.0219mol)。
实施例12
其制备方法与实施例1基本相同，不同之处在于，使用的硅氧烷化合物为3-氨丙基三丙氧基硅烷(0.0219mol)。
对比例1
其制备方法与实施例1基本相同，不同之处在于，不使用3-氨丙基三丙氧基硅烷进行接枝。
表1：实施例中所使用的原料及其所得胶膜的性能
Figure PCTCN2022101486-appb-000011
由表1可以看出，与不进行接枝的共聚物相比(参见对比例1)，接枝了本发明的硅氧烷化合物的共聚物可以实现更好的胶膜性能。
实施例13
正极极片以及二次电池的制备
正极极片制备：取95重量份的磷酸铁锂，2重量份导电炭黑Super P，1重量份的羧甲基纤维素加入到搅拌罐中，加入30重量份去离子水捏合1小时，继续加入70重量份去离子水搅拌1.5小时，之后加入2重量份实施例1中合成的水系粘接剂乳液，继续搅拌1小时，得到水系正极浆料。将所得浆料通过挤压涂布涂覆于铝箔表面(厚度 12μm)，在120℃下烘干5分钟，得到水系正极极片。
负极极片的制备：将负极活性材料人造石墨、导电剂乙炔黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC-Na)按照重量比为95:1:3:1溶于去离子水中，充分搅拌混合均匀后制备成负极浆料；将负极浆料涂覆在负极集流体铜箔上，之后经过烘干、冷压、分切，得到负极极片。
隔离膜：采用聚丙烯膜。
电解液的制备：将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按体积比1:1:1混合，然后将LiPF 6均匀溶解在上述溶液中，得到电解液。该电解液中，LiPF 6的浓度为1mol/L。
二次电池的制备：将上述正极极片、隔离膜、负极极片按顺序堆叠并卷绕，得到电极组件；将电极组件放入外包装中，加入上述制备的电解液，经封装、静置、化成、老化等工序后，得到二次电池。
实施例14
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例2中所合成的粘接剂。
实施例15
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例3中所合成的粘接剂。
实施例16
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例4中所合成的粘接剂。
实施例17
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例5中所合成的粘接剂。
实施例18
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例6中所合成的粘接剂。
实施例19
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例7中所合成的粘接剂。
实施例20
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例8中所合成的粘接剂。
实施例21
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例9中所合成的粘接剂。
实施例22
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例10中所合成的粘接剂。
实施例23
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例11中所合成的粘接剂。
实施例24
其制备方法与实施例13基本相同，不同之处在于，在制备正极极片时，使用的粘接剂为实施例12中所合成的粘接剂。
对比例2
在制备正极极片时，除使用的粘接剂为对比例1的未接枝硅氧烷的聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)外，其他部分与实施例13相同。
表2：所制备的正极极片的性能测试结果
Figure PCTCN2022101486-appb-000012
由表2可以看出，本发明的粘结剂具有更好的粘结性能。出乎意料地，使用本发明粘结剂的二次电池还具有改善的电池容量保持率。

Claims (19)

  1. 粘结剂，其包含接枝聚合物，所述接枝聚合物包含作为主链的式I的共聚物以及接枝在主链上的式II的硅氧烷：
    Figure PCTCN2022101486-appb-100001
    其中R 1、R 2和R 3各自独立地选自氢和C1-C6烷基中的至少一个，可选地各自独立地选自氢和甲基中的至少一个；
    R 4选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)OLi、C(＝O)ONa和CN中的至少一个；
    R 5选自C(＝O)OLi、C(＝O)ONa、CN、C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个，可选地选自C(＝O)NH 2和羰基氧基C1-C6烷基中的至少一个；
    R 6选自COOH、OH、CN和羰基氧基C1-C6烷基羟基中的至少一个，可选地选自OH和羰基氧基C1-C6烷基羟基中的至少一个；
    其中x、y各自独立地为0至5000的整数，可选为500至1500的整数；x和y不同时为0；
    z为100至3000的整数，可选为200至1500的整数；
    Figure PCTCN2022101486-appb-100002
    其中R 7选自C1-C6烯基、C1-C6炔基、C1-C6烷基叠氮基、C1-C6烷基氨基、C1-C6烷基羧基、C1-C6烷基羟基、C1-C6烷基环氧基和C1-C6烷基巯基中的至少一个，可选地选自C1-C6烷基氨基、C1-C6烷基羧基和C1-C6烷基环氧基中的至少一个；
    R 8和R 9各自独立地选自C1-C6烷基和C1-C6烷基氧基中的至少一个；
    R 10为C1-C6烷基。
  2. 根据权利要求1所述的粘结剂，其中所述式I的共聚物在所述接枝聚合物中的重量百分比为90％至99.9％。
  3. 根据权利要求1或2所述的粘结剂，其中所述式II的硅氧烷在所述接枝聚合物中的接枝比例为0.1％至5％。
  4. 根据权利要求1至3中任一项所述的粘结剂，所述式I的共聚物为由三种单体共聚形成的三元共聚物，其中第一单体为(甲基)丙烯酸锂、(甲基)丙烯酸钠或丙烯腈；第二单体为(甲基)丙烯酸C1-C6烷基酯、(甲基)丙烯酰胺或丙烯腈；第三单体为(甲基)丙烯酸羟基C1-C6烷基酯。
  5. 根据权利要求1至4中任一项所述的粘结剂，其中第一单体、第二单体和第三单体的摩尔比为(0.5-3)：(0.5-2)：1，可选为(0.8-2.5)：(0.6-1.5)：1。
  6. 根据权利要求1至5中任一项所述的粘结剂，其中所述三元共聚物选自聚(丙烯酸锂-丙烯酸甲酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酸丙酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酸戊酯-丙烯酸羟甲酯)、聚(丙烯酸锂-丙烯酰胺-丙烯酸羟甲酯)、聚(丙烯睛-丙烯酸甲酯-丙烯酸羟甲酯)和聚(丙烯酸钠-丙烯睛-丙烯酸羟甲酯)中的至少一种。
  7. 根据权利要求1至6中任一项所述的粘结剂，其中所述式II的硅氧烷选自3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷和3-氨丙基三丙氧基硅烷中的至少一种。
  8. 根据权利要求1至7中任一项所述的粘结剂，其中所述粘结剂为水乳液的形式，其中所述接枝聚合物在水乳液中的重量百分比为5％至50％，可选10％至40％。
  9. 根据权利要求1至8中任一项所述的粘结剂，其中所述粘结剂的粘度为100mPa·s至20000mPa·s，可选为500mPa·s至2000 mPa·s。
  10. 一种制备权利要求1至9中所述的粘结剂的方法，其中所述方法包含以下步骤：
    步骤(1)：将式I的共聚物与卤代C1-C6烷基环氧基化合物在碱的存在下进行反应，所述反应在溶剂的存在下进行；
    步骤(2)：在任选地除去溶剂后并加入水，然后再加入式II的硅氧烷和任选地表面活性剂并进行搅拌。
  11. 根据权利要求10所述的方法，其中所述式I的共聚物与卤代C1-C6烷基环氧基化合物的重量比为1:(0.005-0.1)，可选为1:(0.01-0.05)。
  12. 根据权利要求10或11所述的方法，其中所述卤代C1-C6烷基环氧基化合物与式II的硅氧烷的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)；
    可选地，所述卤代C1-C6烷基环氧基化合物为环氧氯丙烷；
    可选地，所述碱选自氢化钠和氢氧化钠中的至少一种，可选为氢化钠；
    可选地，所述卤代C1-C6烷基环氧基化合物与所述碱的摩尔比为1:(0.5-2)，可选为1:(0.8-1.5)，还可选为1:(0.9-1.2)1。
  13. 一种浆料，其包含权利要求1至9中任一项所述的粘结剂或根据权利要求10至12中任一项所述的方法制备的粘结剂。
  14. 根据权利要求13所述的浆料，其中所述浆料包含重量百分比为0.5％至5％的所述粘结剂。
  15. 一种电极极片，其包含集流体和设置在集流体至少一个表面的由权利要求13或14所述的浆料形成的膜层。
  16. 一种二次电池，其包含权利要求15所述的电极极片。
  17. 一种电池模块，包括权利要求16所述的二次电池。
  18. 一种电池包，包括权利要求17的电池模块。
  19. 一种用电装置，包括选自权利要求16所述的二次电池、权利要求17所述的电池模块或权利要求18的电池包中的至少一种。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1953252A (zh) * 2005-10-19 2007-04-25 比亚迪股份有限公司 电池负极和采用该负极的锂离子电池及它们的制备方法
US20140038049A1 (en) * 2012-08-01 2014-02-06 Samsung Sdi Co., Ltd. Binder for electrode of lithium rechargeable battery and electrode for rechargeable battery comprising the same
CN106012492A (zh) * 2016-05-30 2016-10-12 哈尔滨工业大学 一种双官能超支化硅氧烷改善pbo纤维抗紫外性能的方法
CN106220779A (zh) * 2016-08-17 2016-12-14 四川茵地乐科技有限公司 丙烯腈共聚物粘合剂及其在锂离子电池中的应用
CN111725509A (zh) * 2020-06-24 2020-09-29 名添科技（深圳）有限公司 一种负极材料、负极浆料、负极片及锂离子电池
CN113024707A (zh) * 2021-01-28 2021-06-25 江汉大学 一种环保水性硅碳负极粘结剂及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1953252A (zh) * 2005-10-19 2007-04-25 比亚迪股份有限公司 电池负极和采用该负极的锂离子电池及它们的制备方法
US20140038049A1 (en) * 2012-08-01 2014-02-06 Samsung Sdi Co., Ltd. Binder for electrode of lithium rechargeable battery and electrode for rechargeable battery comprising the same
CN106012492A (zh) * 2016-05-30 2016-10-12 哈尔滨工业大学 一种双官能超支化硅氧烷改善pbo纤维抗紫外性能的方法
CN106220779A (zh) * 2016-08-17 2016-12-14 四川茵地乐科技有限公司 丙烯腈共聚物粘合剂及其在锂离子电池中的应用
CN111725509A (zh) * 2020-06-24 2020-09-29 名添科技（深圳）有限公司 一种负极材料、负极浆料、负极片及锂离子电池
CN113024707A (zh) * 2021-01-28 2021-06-25 江汉大学 一种环保水性硅碳负极粘结剂及其制备方法和应用

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