WO2024146063A1 - 粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置 - Google Patents

粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置 Download PDF

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Publication number
WO2024146063A1
WO2024146063A1 PCT/CN2023/098412 CN2023098412W WO2024146063A1 WO 2024146063 A1 WO2024146063 A1 WO 2024146063A1 CN 2023098412 W CN2023098412 W CN 2023098412W WO 2024146063 A1 WO2024146063 A1 WO 2024146063A1
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Prior art keywords
lithium
acrylate
binder
battery
methacrylate
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PCT/CN2023/098412
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English (en)
French (fr)
Inventor
程晓楠
洪海艺
李雷
杨建瑞
康海杨
郑义
孙成栋
Original Assignee
宁德时代新能源科技股份有限公司
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Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to KR1020247000834A priority Critical patent/KR20240110791A/ko
Priority to EP23875913.8A priority patent/EP4418369A1/en
Priority to US18/626,973 priority patent/US20240250315A1/en
Publication of WO2024146063A1 publication Critical patent/WO2024146063A1/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42Nitriles
    • C08F220/44Acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • H01M10/0404Machines for assembling batteries
    • H01M10/0409Machines for assembling batteries for cells with wound electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • H01M10/0413Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42Acrylic resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/443Particulate material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/446Composite material consisting of a mixture of organic and inorganic materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/10Batteries in stationary systems, e.g. emergency power source in plant
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present application relates to the field of battery technology, and in particular to a binder and a preparation method thereof, a separator, a pole piece, an electrode assembly, a battery cell, a battery and an electrical device.
  • Batteries have been widely used in automotive power, power storage, portable electronic products and power tools.
  • the formation of SEI film on the negative electrode surface, the presence of some dead lithium and other impurities in the positive electrode material and other side reactions reduce the efficiency of the first charge and discharge, affecting the cycle performance and rate performance of the battery.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a binder with good bonding performance, which also has a lithium replenishing effect, thereby helping to reduce electrochemical impedance and improve the cycle performance and rate performance of lithium-ion batteries.
  • the present application provides a binder and a preparation method thereof, a separator, a pole piece, an electrode assembly, a battery cell, a battery and an electrical device.
  • the consumed lithium ions can be quickly replenished in the lithium battery, the ion transfer rate is increased, and the structural stability of the lithium-ion battery during the cycle is improved.
  • the binder is coated on the diaphragm or the pole piece and applied to the lithium-ion battery, which improves the kinetic performance of the lithium-ion battery, reduces the electrochemical impedance, and can improve the cycle performance and rate performance of the lithium-ion battery.
  • the molar ratio of the acrylate monomer, the acrylonitrile monomer and the acrylamide monomer is 1:(0.01-0.8):(0.01-0.15), optionally 1:(0.05-0.7):(0.05-0.12).
  • the molar ratio of the above three monomers is controlled within the above range, and the molecular weight and glass transition temperature of the polymer are further controlled, thereby improving the bonding performance of the adhesive.
  • the acrylate monomer includes at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; the acrylonitrile monomer includes at least one of acrylonitrile and methacrylonitrile; the acrylamide monomer includes at least one of acrylamide, N-hydroxymethyl acrylate
  • the volume average particle size Dv50 of the binder is ⁇ 50 ⁇ m, and optionally, Dv50 is 7 to 8 ⁇ m. Within the above particle size range, the bonding and lithium supplementation effects are good.
  • Acrylate monomers can improve the anti-swelling ability of polymers, and as flexible monomer segments in the molecular chain segments, they can adjust the glass transition temperature of the polymer, improve the toughness of the adhesive when applied, and help to play a good bonding role; acrylonitrile monomers have a strong polar cyano group, which helps to improve ion conductivity; acrylamide monomers play a role in regulating molecular weight.
  • the simultaneous presence of the above three monomers can control the molecular weight and glass transition temperature of the polymer, thereby improving the bonding performance of the adhesive.
  • the molar ratio of the acrylate monomer, the acrylonitrile monomer and the acrylamide monomer is 1:(0.01-0.8):(0.01-0.15), optionally 1:(0.05-0.7):(0.05-0.12).
  • the molar ratio of the above three monomers is controlled within the above range, and the molecular weight and glass transition temperature of the polymer are further controlled, thereby improving the bonding performance of the adhesive.
  • the step of adding an initiator to the pre-emulsion to react to obtain a reaction solution comprises:
  • the pre-emulsion is added to the second emulsifier solution, and an initiator is added to react to obtain a reaction solution.
  • the reactants are mixed more evenly, the reaction is sufficient, and the product distribution is also more uniform.
  • the lithium-containing substance includes at least one of lithium hydroxide, lithium oxide, lithium carbonate and elemental lithium.
  • the above lithium-containing substance is used as a pH regulator.
  • the pH regulator is saved, the addition of chemical substances is reduced, and the probability of side reactions is reduced.
  • the Li content of the binder can be increased, the consumed lithium ions can be quickly replenished in the lithium battery, the ion transmission rate can be increased, and the lithium ion battery can be improved. Structural stability during pool cycling.
  • an embodiment of the present application provides an isolation film, comprising the adhesive of the embodiment of the first aspect of the present application or an adhesive prepared by the adhesive preparation method described in the embodiment of the second aspect.
  • an embodiment of the present application proposes an electrode assembly, comprising the adhesive of the embodiment of the first aspect of the present application, the adhesive prepared by the adhesive preparation method described in the embodiment of the second aspect, the isolation film of the embodiment of the third aspect, and at least one of the pole pieces of the embodiment of the fourth aspect.
  • FIG2 is an exploded view of a battery cell according to an embodiment of the present application shown in FIG1 ;
  • FIG3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 6 is a schematic diagram of an electrical device using a secondary battery as a power source according to an embodiment of the present application
  • FIG. 7 is a SEM image of the adhesive of Example 1 of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the diaphragm layer is a polymer film, a metal lithium layer, and a protective layer; the lithium coating diaphragm is a diaphragm coated with glue on one side of the base film and a lithium replenishing slurry on the other side. After drying in an oven, a lithium replenishing composite diaphragm is obtained; the ceramic composite diaphragm is a diaphragm with a ceramic layer and a ceramic-replenishing slurry on both sides of the base film.
  • the lithium layer can replenish the consumed lithium ions in time, increase the ion transfer rate, and improve the structural stability of the lithium battery during the cycle.
  • These methods all have independent metal lithium layers or lithium replenishment layers. Although they can improve the dynamics, they will affect the adhesion between the diaphragm and the pole piece, and affect the cycle performance and rate performance of the battery.
  • the applicant consulted a large amount of information and conducted a large number of experiments, and thought that if the lithium replenisher and the binder could be combined into one material, there would be no need to set up an additional lithium replenisher layer, thereby solving the problem of affecting the adhesion between the diaphragm and the electrode, and affecting the cycle performance and rate performance of the battery.
  • the monomers of the polyacrylate copolymer include acrylic acid ester monomers, acrylonitrile monomers and acrylamide monomers.
  • R1 includes hydrogen atom or alkyl group of 1 to 6 carbon atoms
  • R2 includes substituted or unsubstituted alkyl group of 1 to 15 carbon atoms, cycloalkyl group of 3 to 6 carbon atoms or isobornyl group, and in the case of substitution, the substituent includes hydroxyl group or alkyl group of 1 to 6 carbon atoms.
  • the step of adding an initiator to the pre-emulsion to react to obtain a reaction solution comprises:
  • the first emulsifier and the second emulsifier can be emulsifiers commonly used in the art, such as sodium dodecyl sulfate, and the present application does not limit this.
  • the first emulsifier and the second emulsifier can be the same or different, and the present application does not limit this.
  • reaction temperature and reaction time can satisfy only one of them or both. In the embodiments of the present application, both are satisfied at the same time, which makes the reaction more complete and has fewer side reactions.
  • step a lithium-containing substance is added to the reaction solution to make the pH value of the reaction solution 7 to 8, and the binder is obtained by filtering.
  • the mass ratio of lithium to the polyacrylate copolymer is 1:(10-1000), which can be, for example but not limited to, any one of 1:10, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000 or any range between two of them. Under the above ratio, the pH value adjustment and lithium supplementation effects are better.
  • the binder of the first aspect of the present application When the binder of the first aspect of the present application is applied to the isolation membrane, it helps to reduce the resistance of the isolation membrane, increase the ion conductivity of the isolation membrane, thereby improving battery performance, and can also play a role in effectively replenishing lithium.
  • the present application has no particular limitation on the type of the isolation membrane substrate, and any known isolation membrane substrate with a porous structure having good chemical stability and mechanical stability can be selected.
  • the isolation film described in the present application can be prepared by conventional methods for isolation films in the art.
  • the binder described in the first aspect of the present application can be dissolved in an organic solvent to obtain a slurry, and then the slurry can be coated on the isolation film material, and then the organic solvent can be removed by thousands of times to obtain the isolation film described in the present application.
  • the present application proposes a pole piece, comprising the adhesive of the first aspect embodiment of the present application or the adhesive prepared by the method for preparing the adhesive described in the second aspect embodiment. It comprises the adhesive described in the first aspect embodiment of the present application or the adhesive prepared by the method for preparing the adhesive described in the second aspect embodiment.
  • the electrode pole piece can be prepared by methods commonly used in the art.
  • the electrode plate described in the present application can be a positive electrode plate or a negative electrode plate.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the positive electrode film layer includes the binder of the first aspect of the present application.
  • the positive electrode current collector has two surfaces opposite to each other in its 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 may be used.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.) on a substrate.
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material for a battery known in the art.
  • the positive electrode 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 for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more.
  • the phosphate containing lithium ion battery may be abbreviated as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also abbreviated as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also abbreviated as NCM 811 ), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O 2 ) and modified compounds thereof.
  • lithium phosphate containing olivine structure may include but are not limited to lithium iron phosphate (such as LiFePO 4 (also abbreviated as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also abbreviated as LFP)
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate and carbon
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder described in the first aspect of the present application, and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the amount of the binder described in the embodiment of the first aspect of the present application in the positive electrode plate is 1-3%, based on the total weight of the positive electrode film layer.
  • the electrode plate described in the present application may also be a negative electrode plate.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes the binder described in the first aspect of the present application.
  • the negative electrode current collector has two surfaces opposite to each other in its 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 metal foil copper foil may 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 substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.) on a substrate.
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
  • the negative electrode 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, etc.
  • 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 negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further include a conductive agent, which may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • a conductive agent which 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 may also optionally include other additives, such as a thickener (such as a carboxylic acid
  • CMC-Na Sodium methylcellulose
  • the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the The binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the amount of the binder described in the embodiment of the first aspect of the present application in the negative electrode plate is 1-3%, based on the total weight of the negative electrode film layer.
  • a battery cell includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator.
  • active ions are embedded and released back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the separator is set between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the battery cell may include an outer packaging.
  • the outer packaging may be used to encapsulate the above Electrode assembly and electrolyte.
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the battery cell 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the embodiments of the present application provide a battery, including the battery cell of the embodiment of the sixth aspect of the present application.
  • the specific form of the battery can be a battery module and a battery pack, and the number of battery cells contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • an embodiment of the present application provides an electrical device, comprising a battery cell of an embodiment of the sixth aspect of the present application or a battery of an embodiment of the seventh aspect.
  • a commercially available PP-PE copolymer microporous film with a thickness of 20 ⁇ m and an average pore size of 80 nm was used as the substrate.
  • the binder prepared as described above was stirred and mixed uniformly in deionized water to obtain a slurry (solid content of 20%).
  • the slurry was evenly coated on both surfaces of the substrate, and dried to remove the solvent.
  • the coating density of the coating composition on the substrate was 1.0 g/m 2 to obtain a separator.
  • PVDF Polyvinylidene fluoride
  • LFP lithium iron phosphate
  • NMP N-methylpyrrolidone
  • the binder is coated on the diaphragm or the pole piece and applied to the lithium-ion battery, which improves the kinetic performance of the lithium-ion battery, reduces the electrochemical impedance, and can improve the cycle performance and rate performance of the lithium-ion battery.

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Abstract

本申请公开一种粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置,涉及电池技术领域。所述粘结剂包括聚丙烯酸酯类共聚物和含锂化合物。所述粘结剂包括聚丙烯酸酯类共聚物和含锂化合物,使得聚合物具有很好的抗溶胀能力,并有助于发挥良好的粘结作用,提高离子电导率,控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。粘结剂还包括含锂化合物,使粘结剂同时具有粘结剂和补锂剂两个作用,无需在锂离子电池中设置独立的金属锂层或补锂层,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。

Description

粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置
相关申请的交叉引用
本申请要求享有于2023年01月04日提交的名称为“粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置”的中国专利申请202310009976.4的优先权,该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及电池技术领域,具体涉及一种粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置。
背景技术
电池在汽车动力、电力储能、便携式电子产品和电动工具等方面得到了广泛的应用。在电池的首次充放电过程中,由于在负极表面生成SEI膜,正极材料一些死锂及其它杂质副反应的存在等问题,降低了首次充放电的效率,影响电池的循环性能和倍率性能。
发明内容
本申请是鉴于上述课题而进行的,其目的在于,提供一种具有良好的粘结性能的粘结剂,该粘结剂还具有补锂效果,从而有助于降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
为了达到上述目的,本申请提供一种粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置。
第一方面,本申请实施例提出了一种粘结剂,包括聚丙烯酸酯类共聚物和含锂化合物。
由此,本申请实施例的技术方案中,所述粘结剂包括聚丙烯酸酯类共聚物和含锂化合物,使得聚合物具有很好的抗溶胀能力,并有助于发挥良好的粘结作用,提高离子电导率,控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。此外,粘结剂还包括含锂化合物,使粘结剂同时具有粘结剂和补锂剂两个作用,无需在锂离子电池中设置独立的金属锂层或补锂层,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性,该粘结剂涂覆在隔膜或极片上应用到锂离子电池上,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
由此,丙烯酸酯类单体可提高聚合物抗溶胀能力,并且作为分子链段中的柔性单体链段能够调节聚合物的玻璃化转变温度,改善粘结剂在施用时的韧性,有助于发挥良好的粘结作用;丙烯腈类单体具有强极性的氰基基团,有助于提高离子电导率;丙烯酰胺类单体起到调节分子量的作用。上述三种单体的同时存在,可控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15),可选地为1:(0.05~0.7):(0.05~0.12)。上述三种单体的摩尔比例控制上述范围内,进一步控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;所述丙烯腈类单体包括丙烯腈和甲基丙烯腈中的至少一种;所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种,实验表明,三种单体采用上述物质,补锂和粘结效果好,进一步提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可选地为1:(100-600),上述配比下,使得所述粘结剂能够同时具有优秀的补锂和粘结效果。
在任意实施方式中,所述粘结剂的体积平均粒径Dv50≤50μm,可选地,Dv50为7~8μm。上述粒径范围内,粘结和补锂效果好。
第二方面,本申请实施例提出一种粘结剂的制备方法,包括:
将聚丙烯酸酯类共聚物的单体加入第一乳化剂溶液中,得预乳化液;
向所述预乳化液中加入引发剂进行反应,得反应液;
向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂。
通过乳液聚合,聚合速度快,有利于传热控温,反应达高转化率后乳聚体系的粘度仍很低,分散体系稳定,较易控制和实现连续操作。此外,将含锂物质作为pH值调节剂,一方面节省了pH值调节剂,减少了化学物质的加入,降低副反应发生概率,另一方面,能够提高粘结剂的Li含量,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性。该粘结剂涂覆在隔膜上应用到锂离子电池上,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,在步骤将聚丙烯酸酯类共聚物的单体加入第一乳化 剂溶液中,得预乳化液中,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
丙烯酸酯类单体可提高聚合物抗溶胀能力,并且作为分子链段中的柔性单体链段能够调节聚合物的玻璃化转变温度,改善粘结剂在施用时的韧性,有助于发挥良好的粘结作用;丙烯腈类单体具有强极性的氰基基团,有助于提高离子电导率;丙烯酰胺类单体起到调节分子量的作用。上述三种单体的同时存在,可控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15),可选地为1:(0.05~0.7):(0.05~0.12)。上述三种单体的摩尔比例控制上述范围内,进一步控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;所述丙烯腈类单体包括丙烯腈和甲基丙烯腈中的至少一种;所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种,实验表明,三种单体采用上述物质,补锂和粘结效果好,进一步提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可选地为1:(100-600),上述配比下,使得所述粘结剂能够同时具有优秀的补锂和粘结效果。
在任意实施方式中,步骤向所述预乳化液中加入引发剂进行反应,得反应液包括:
在加热回流条件下,将所述预乳化液加入第二乳化剂溶液中,加入引发剂反应,得反应液。
通过第一乳化剂和第二乳化剂,使得反应物混合更加均匀,反应充分,进而产物分布也更加均匀。
在任意实施方式中,所述反应的温度为20~90℃,所述反应的时间为20~40min,实验表明,上述反应温度和时间下,反应更加充分,副反应少。
在任意实施方式中,在步骤向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂中,
所述含锂物质包括氢氧化锂、氧化锂、碳酸锂及单质锂中的至少一种,采用上述含锂物质作为pH值调节剂,一方面节省了pH值调节剂,减少了化学物质的加入,降低副反应发生概率,另一方面,能够提高粘结剂的Li含量,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电 池循环过程中的结构稳定性。
锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可选地为1:(100-600),上述配比下,使得调节pH值和补锂效果更好。
第三方面,本申请实施例提出了一种隔离膜,包括本申请第一方面实施例的粘结剂或者通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂。
第四方面,本申请实施例提出了一种极片,包括本申请第一方面实施例的粘结剂或者通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂。
第五方面,本申请实施例提出了一种电极组件,包括本申请第一方面实施例的粘结剂、通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂、第三方面实施例的隔离膜和第四方面实施例的极片中的至少一种。
第六方面,本申请实施例提供了一种电池单体,包括本申请第五方面实施例的电极组件。
第七方面,本申请实施例提供了一种电池,包括本申请第六方面实施例的电池单体。
第八方面,本申请实施例提供了一种用电装置,包括本申请第六方面实施例的电池单体或者第七方面实施例的电池。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅为本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1是本申请一实施方式的电池单体的示意图;
图2是图1所示的本申请一实施方式的电池单体的分解图;
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为本申请实施例1的粘结剂的SEM图。
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。
本发明目的的实现、功能特点及优点将结合实施例,参照附图做进一步
说明。
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、隔离膜、极片、电极组件、电池单体、电池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,本申请的所有步骤可以顺序进行,也可以随机进行,优选是顺序进行的。例如,所述方法包括步骤(a)和(b),表示所述方法可包括顺序进行的步骤(a)和(b),也可以包括顺序进行的步骤(b)和(a)。例如,所述提到所述方法还可包括步骤(c),表示步骤(c)可以任意顺序加入到所述方法,例如,所述方法可以包括步骤(a)、(b)和(c),也可包括步骤(a)、(c)和(b),也可以包括步骤(c)、(a)和(b)等。
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)。
锂离子电池在汽车动力、电力储能、便携式电子产品和电动工具等方面得到了广泛的应用。在锂离子电池的首次充放电过程中,由于在负极表面生成SEI膜,正极材料一些死锂及其它杂质副反应的存在等问题,降低了首次充放电的效率。在隔膜上补锂,主要方法有预制锂层隔膜,补锂隔膜包括若干的相互叠加的隔膜层,隔膜层为聚合物膜、金属锂层、保护层;锂涂层隔膜,是在基膜一侧涂覆胶液,另一侧表面涂覆补锂浆料,在烘箱中烘干后得到补锂复合隔膜;陶瓷复合隔膜,是在基膜两侧分别设置有陶瓷层和陶瓷-补 锂层,能及时补充消耗的锂离子,增大离子传输速率,提高锂电池循环过程中的结构稳定性。这些方法都是存在独立的金属锂层或补锂层,虽然能提高动力学,但会对隔膜与极片粘结力产生影响,对电池的循环性能、倍率性能产生影响。
也就是说,发明人在实际工作中发现,现有技术中使用的电池用补锂剂会对隔膜与极片粘结力产生影响,对电池的循环性能、倍率性能产生影响。
基于此,申请人在查阅大量资料和进行大量实验,思考到,如果能将补锂剂和粘结剂这两者结合成一个材料,便可无需额外设立补锂层,从而解决了对隔膜与极片粘结力产生影响,对电池的循环性能、倍率性能产生影响的问题。
进一步地,发明人在进行大量实验后发现,通过将包含特定官能团的聚合物单体以一定的重量比进行聚合而获得的有机聚合物具备良好的粘结性能,并且适于在电池作业条件下充分发挥其粘结性能,从而有助于提升二次电池的动力学性能和安全性能。此外,当所述粘结剂应用于隔离膜时,有助于降低隔离膜的电阻,提升隔离膜的离子电导率,从而改善电池性能。
从市场形势的发展来看,动力电池的应用越加广泛。动力电池不仅被应用于水力、火力、风力和太阳能电站等储能电源系统,而且还被广泛应用于电动自行车、电动摩托车、电动汽车等电动交通工具,以及军事装备和航空航天等多个领域。随着动力电池应用领域的不断扩大,其市场的需求量也在不断地扩增。
基于此,本申请提供一种粘结剂、隔离膜、极片、电极组件、电池单体、电池及用电装置。
第一方面,本申请实施例提出了一种粘结剂,包括聚丙烯酸酯类共聚物和含锂化合物。
聚丙烯酸酯类共聚物是以丙烯酸酯为原料经共聚反应生成的聚合物的总称。丙烯酸醋具有活泼的双键,易自聚,亦易共聚。共聚单体可以是一种或多种,可以是另外的丙烯酸系化合物或其他带双键的不饱和化合物,例如苯乙烯、丙烯睛、醋酸乙烯、氯乙烯等。
含锂化合物是含有锂的化合物,可以是有机物,也可以是无机物,只要含有锂元素,均在本申请的保护范围内。
由此,本申请实施例的技术方案中,所述粘结剂包括聚丙烯酸酯类共聚物和含锂化合物,使得聚合物具有很好的抗溶胀能力,并有助于发挥良好的粘结作用,提高离子电导率,控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。此外,粘结剂还包括含锂化合物,使粘结剂同时具有粘结剂和补锂剂两个作用,无需在锂离子电池中设置独立的金属锂层或补锂层,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性,该粘结剂涂覆在隔膜或极片上应用到锂离子电池上,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
丙烯酸酯类单体是包含丙烯酸酯基的单体,其结构简式如下:
其中,R1包括氢原子或1~6个碳原子的烷基,R2包括取代或未取代的1~15个碳原子的烷基、3~6个碳原子的环烷基或异冰片基,在取代的情况下,取代基包括羟基或1~6个碳原子的烷基。
丙烯腈类单体是包含丙烯腈基的单体,其结构简式如下:
其中,R3包括氢原子或1~6个碳原子的烷基。
丙烯酰胺类单体是包含丙烯酰氨基的单体,其结构简式如下:
其中,R4包括氢原子或1~6个碳原子的烷基,R5包括氢原子、羟基取代的1~6个碳原子的烷基或1~6个碳原子的烷氧基。
由此,丙烯酸酯类单体可提高聚合物抗溶胀能力,并且作为分子链段中的柔性单体链段能够调节聚合物的玻璃化转变温度,改善粘结剂在施用时的韧性,有助于发挥良好的粘结作用;丙烯腈类单体具有强极性的氰基基团,有助于提高离子电导率;丙烯酰胺类单体起到调节分子量的作用。上述三种单体的同时存在,可控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
可以理解的是,本申请对于聚丙烯酸酯类共聚物中,各个单体的排序方式不作限制,可以是丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体三者依次顺序排布,也可以是三者无序排布,上述方式均在本申请的保护范围内。
在任意实施方式中,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15)。可以例如但不限于为1:0.01:0.01、1:0.01:0.15、1:0.8:0.01、1:0.8:0.15、1:0.4:0.01、1:0.4:0.15、1:0.01:0.08、1:0.8:0.08中的任意一者点值或者任意两者之间的范围值。上述三种单体的摩尔比例控制上述范围内,进一步控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、 丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;所述丙烯腈类单体包括丙烯腈和甲基丙烯腈中的至少一种;所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种,实验表明,三种单体采用上述物质,补锂和粘结效果好,进一步提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可以例如但不限于为1:10、1:100、1:200、1:300、1:400、1:500、1:600、1:700、1:800、1:900、1:1000中的任意一者点值或者任意两者之间的范围值。上述配比下,使得所述粘结剂能够同时具有优秀的补锂和粘结效果。
锂是指含锂化合物中的锂,可以理解的是,本申请实施例中,锂与所述聚丙烯酸酯类共聚物通过聚合物离子键的方式连接,锂在所述粘结剂中以化合物的方式存在。
在任意实施方式中,所述粘结剂的体积平均粒径Dv50≤50μm,在本申请实施例中,Dv50为7~8μm。上述粒径范围内,粘结和补锂效果好。
在本申请实施例中,粘结剂颗粒累计粒度分布百分数达到50%时所对应的粒径为Dv50,测试方法为:
参考标准GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法。使用激光粒度仪(马尔文3000,MasterSizer 3000)测试,主光源使用氦氖红光光源。取一洁净小烧杯加入待测样品1g,加入一滴表面活性剂,加入20ml去离子水(样品浓度保证遮光度为8~12%),以53KHz/120W超声5min,确保样品完全分散。打开激光粒度仪,清洗光路系统后,自动测试背景。搅拌已超声的待测溶液,使其分散均匀,按要求放入样品池中,开始测量粒径。从仪器中即可读得测量结果。
第二方面,本申请实施例提出一种粘结剂的制备方法,包括:
将聚丙烯酸酯类共聚物的单体加入第一乳化剂溶液中,得预乳化液;
向所述预乳化液中加入引发剂进行反应,得反应液;
向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂。
乳化剂是一类能使互不相溶的液体形成稳定乳状液的有机化合物。它们都是具有表面活性的物质,能降低液体间的界面张力,使互不相溶的液体易于乳化。乳化时,分散相是以很小的液珠形式(直径在0.1微米至几十微米之间)均匀地分布在连续相中,乳化剂在这些液珠的表面上形成薄膜或双电层,以阻止它们的相互凝聚,保持乳状液的稳定。本申请实施例中,采用的乳化剂为十二烷基磺酸钠。
预乳化液是将聚丙烯酸酯类共聚物的单体乳化后形成的溶液,使得各单体形成稳定的乳状液。
引发剂又称自由基引发剂,指一类容易受热分解成自由基(即初级自由基) 的化合物,可用于引发烯类、双烯类单体的自由基聚合和共聚合反应,也可用于不饱和聚酯的交联固化和高分子交联反应。在本申请实施例中,采用的引发剂是过硫酸钾。
氢离子浓度指数的数值俗称“pH值”。表示溶液酸性或碱性程度的数值,即所含氢离子浓度的常用对数的负值。pH值测定可以采用pH试纸,也可以采用pH测定仪。
通过乳液聚合,聚合速度快,有利于传热控温,反应达高转化率后乳聚体系的粘度仍很低,分散体系稳定,较易控制和实现连续操作。此外,将含锂物质作为pH值调节剂,一方面节省了pH值调节剂,减少了化学物质的加入,降低副反应发生概率,另一方面,能够提高粘结剂的Li含量,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性。该粘结剂涂覆在隔膜上应用到锂离子电池上,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
本领域技术人员可以理解,在具体实施例的上述方法中,各步骤的撰写顺序并不意味着严格的执行顺序而对实施过程构成任何限定,各步骤的具体执行顺序应当以其功能和可能的内在逻辑确定。
在任意实施方式中,在步骤将聚丙烯酸酯类共聚物的单体加入第一乳化剂溶液中,得预乳化液中,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
丙烯酸酯类单体可提高聚合物抗溶胀能力,并且作为分子链段中的柔性单体链段能够调节聚合物的玻璃化转变温度,改善粘结剂在施用时的韧性,有助于发挥良好的粘结作用;丙烯腈类单体具有强极性的氰基基团,有助于提高离子电导率;丙烯酰胺类单体起到调节分子量的作用。上述三种单体的同时存在,可控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15)。
单体的摩尔比为单体的摩尔数之比,可以例如但不限于为1:0.01:0.01、1:0.01:0.15、1:0.8:0.01、1:0.8:0.15、1:0.4:0.01、1:0.4:0.15、1:0.01:0.08、1:0.8:0.08中的任意一者点值或者任意两者之间的范围值。上述三种单体的摩尔比例控制上述范围内,进一步控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。
在任意实施方式中,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;所述丙烯腈类单体 包括丙烯腈和甲基丙烯腈中的至少一种;所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种,实验表明,三种单体采用上述物质,补锂和粘结效果好,进一步提高锂离子电池的循环性能和倍率性能。
在任意实施方式中,锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可以例如但不限于为1:10、1:100、1:200、1:300、1:400、1:500、1:600、1:700、1:800、1:900、1:1000中的任意一者点值或者任意两者之间的范围值。上述配比下,使得所述粘结剂能够同时具有优秀的补锂和粘结效果。
在任意实施方式中,步骤向所述预乳化液中加入引发剂进行反应,得反应液包括:
在加热回流条件下,将所述预乳化液加入第二乳化剂溶液中,加入引发剂反应,得反应液。
通过第一乳化剂和第二乳化剂,使得反应物混合更加均匀,反应充分,进而产物分布也更加均匀。
可以理解,在本申请实施例中,所述第一乳化剂和第二乳化剂可以是本领域常见的乳化剂,例如十二烷基磺酸钠,本申请对此不作限制,此外,所述一乳化剂和第二乳化剂可以相同,也可以不同,本申请对此也不作限制。
在任意实施方式中,所述反应的温度为20~90℃,可以例如但不限于为20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃中的任意一者点值或者任意两者之间的范围值。所述反应的时间为20~40min,可以例如但不限于为20min、22min、25min、28min、30min、33min、35min、37min、40min中的任意一者点值或者任意两者之间的范围值。实验表明,上述反应温度和时间下,反应更加充分,副反应少。
可以理解,上述反应温度和反应时间的限制,可以只满足其中一个,也可以同时满足,在本申请实施例中,两者同时满足,是的反应更充分,副反应更少。
在任意实施方式中,在步骤向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂中,
所述含锂物质包括氢氧化锂、氧化锂、碳酸锂及单质锂中的至少一种,上述含锂物质均呈碱性,能够起到调节反应液pH值的作用,采用上述含锂物质作为pH值调节剂,一方面节省了pH值调节剂,减少了化学物质的加入,降低副反应发生概率,另一方面,能够提高粘结剂的Li含量,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性。
锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可以例如但不限于为1:10、1:100、1:200、1:300、1:400、1:500、1:600、1:700、1:800、1:900、1:1000中的任意一者点值或者任意两者之间的范围值。上述配比下,使得调节pH值和补锂效果更好。
第三方面,本申请实施例提出了一种隔离膜,包括本申请第一方面实施 例的粘结剂或者通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂。
当本申请第一方面的粘结剂应用于隔离膜时,有助于降低隔离膜的电阻,提升隔离膜的离子电导率,从而改善电池性能,还能起到有效补锂的作用。
本申请对隔离膜基材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基材。
在一些实施方式中,隔离膜基材可选自玻璃纤维、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。
本申请所述隔离膜可采用本领域隔离膜的常规方法制备。例如,可将本申请第一方面所述的粘结剂溶于有机溶剂中,得到浆液,然后将浆液涂布在隔离膜材质上,随后经千重除去有机溶剂,即可得到本申请所述的隔离膜。
在一些实施方式中,粘结剂在隔离膜基材上的涂布密度为0.3-1.0g/m2,进一步为0.3-0.8g/m2
第四方面,本申请提出了一种极片,包括本申请第一方面实施例的粘结剂或者通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂。其包括本申请第一方面实施例所述的粘结剂或者通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂。电极极片可通过本领域通常使用的方法制备。
需要说明的是,本申请所述电极极片可以是正极极片或负极极片。
正极极片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,所述正极膜层包括本申请第一方面的粘结剂。
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,所述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LiCoO2),锂镍氧化物(如LiNiO2),锂锰氧化物(如LiMnO2,LiMn2O4),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LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333),LiNi0.5Co0.3Mn0.2O2(也可以简称为NCM523),LiNi0.5Co0.25Mn0.25O2(也 可以简称为NCM211),LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622),LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811),锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)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LiFePO4(也可以简称为LFP)),磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4),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,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、本申请第一方面实施例所述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。
在一些实施方式中,本申请第一方面实施例所述的粘结剂在正极极片中的用量为1-3%,基于正极膜层的总重量计。
类似地,本申请所述电极极片也可以是负极极片。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,所述负极膜层包括本申请第一方面所述的粘结剂。
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,所述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。所述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。所述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,负极膜层还可选地包括导电剂。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,例如增稠剂(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、本申请第一方面实施例所述 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。
在一些实施方式中,本申请第一方面实施例所述的粘结剂在负极极片中的用量为1-3%,基于负极膜层的总重量计。
第五方面,本申请实施例提出了一种电极组件,包括本申请第一方面实施例的粘结剂、通过第二方面实施例所述的粘接剂的制备方法制得的粘接剂、第三方面实施例的隔离膜和第四方面实施例的极片中的至少一种。本申请提出的电极组件,具备了上述粘结剂的全部有益效果,在此不再一一赘述。
第六方面,本申请实施例提供了一种电池单体,包括本申请第五方面实施例的电极组件。
通常情况下,电池单体包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中,活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间,主要起到防止正负极短路的作用,同时可以使离子通过。
电池单体的制备可通过本领域通常使用的方法进行,例如,可将正极极片、负极极片和隔离膜通过卷绕工艺或叠片工艺制成电极组件,然后向电极组件中注入电解液并密封而制得电池单体。
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,所述电解质采用电解液。所述电解液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、双氟磺酞亚胺锂、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,所述电解液还可选地包括添加剂。例如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。
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,电池单体可包括外包装。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,电池单体的外包装可以是硬壳,例如硬塑料壳、铝壳、钢壳等。电池单体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。
本申请对电池单体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电池单体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。电池单体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。
第七方面,本申请实施例提供了一种电池,包括本申请第六方面实施例的电池单体。电池的具体表现形式可以为电池模块和电池包,电池模块所含电池单体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,多个电池单体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电池单体5进行固定。
在任意实施方式中,电池模块4还可以包括具有容纳空间的外壳,多个电池单体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。
第八方面,本申请实施例提供了一种用电装置,包括本申请第六方面实施例的电池单体或者第七方面实施例的电池。
所述电池单体和电池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。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化,可以采用二次电池作为电源。
以下结合具体实施例和附图对本发明的技术方案作进一步详细说明,应当理解,以下实施例仅用以解释本发明,并不用于限定本发明。
上述实施例1~17、对比例1~2的粘结剂的相关参数如下述表1所示。
表1:实施例1~17与对比例1~2的参数
实施例1
【粘结剂的制备】
(1)向500ml三口瓶中分别加入150g的去离子水,3.6g十二烷基磺酸钠,充分搅拌15min进行乳化,然后依次加入75.24g丙烯酸甲酯,18.55g丙烯腈,6.21g丙烯酰胺,三者摩尔比为1:0.4:0.1,充分搅拌60min,得到单体的预乳化液,取出备用;
(2)向500ml三口瓶中加入100ml去离子水、0.15g十二烷基苯磺酸钠,加热至80℃,以2000r/min的转速进行乳化15min,使体系乳化充分,然后缓慢滴加步骤(1)制备的预乳化液及引发剂溶液(将引发剂0.2g过硫酸钾溶于30g去离子水中形成溶液),待滴加完毕后升温到90℃并保温反应0.5h,冷却到40℃;
(3)用LiOH水溶液调节pH值至7后,停止搅拌,过滤,出料。
【隔离膜的制备】
采用市售的厚度为20μm、平均孔径为80nm的PP-PE共聚物微孔薄膜(来自卓高电子科技公司,型号20)作为基材。将如上文制备的粘结剂于去离子水中搅拌混合均匀,得到浆料(固含量为20%)。将浆料均匀涂布在基材的两个表面上,干燥除去溶剂,涂覆组合物在基材上的涂布密度为1.0g/m2,得到隔离膜。
【正极极片的制备】
将聚偏二氟乙烯(PVDF)、磷酸铁锂(LFP)、导电剂碳黑、N-甲基吡咯烷酮(NMP)按质量比为1.2:58.38:0.42:40,充分搅拌混合均匀后制备成正极浆料。将该正极浆料以200g/m2的负载量均匀涂覆在正极集流体铝箔上,之后经过烘干、冷压、分切,得到正极极片。
【负极极片的制备】
将人造石墨、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)按照质量比为96.2:1.0:1.6:1.2,加入去离子水中,充分搅拌混合均匀后制备成负极浆料(固含量为63%)。将该负极浆料以98g/m2的负载量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。
【电解液的制备】
在25℃,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混合得到混合溶剂,然后将LiPF6溶解在上述混合溶剂中,得到电解液,其中LiPF6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、预压成型(在此期间隔离膜与极片粘结),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2至17及对比例1至2的粘结剂及隔离膜、正极极片、负极极片、电解液及二次电池的制备同实施例1,不同之处在于按照表1的参数制备。
对比例1的粘结剂中没有锂,对比例2的粘结剂粒径超过50μm。
将实施例1得到的粘结剂做扫描电镜图,得图7,可以看出,本申请实施例1制得的粘结剂整体呈球形,粒径在8μm左右。
将实施例1至17、对比例1至2的产品进行如下测试:
1、隔膜与极片粘结力测试:
将电池极片与隔离膜重叠在一起,置于热压机上,设定热压机参数为:温度为25℃,压力为10t,时间为30s,施压制得粘结的隔离膜/正极片样品;将隔离膜/极片样品裁切成150×20mm的矩形样条。通过双面胶将上述矩形样条的极片一面粘贴在钢板上,在矩形样条的一端将隔离膜与极片沿长度方向分开2cm的长度,制得测试试样。
将钢板保持水平并用万能试验机(协强仪器制造(上海)有限公司,型号CTM2100)下方夹具固定,将如上所述的隔离膜的剥离端部用万能试验机的上方夹具固定,并连接拉力机。设置测试条件为拉伸速率20mm/min,水平拉动10cm。待拉力稳定后,记录拉力值,通过拉力值与样品宽度的比值,得到隔离膜与极片粘结力。
2、EIS数据(电化学阻抗谱):
采用上海辰华公司的CHI660D型电化学工作站,对电池系统施加频率为W1小振幅的正弦波电压信号,系统会产生一个频率为W2的正弦波电流响应,激励电压与响应电流的比值变化即为电化学系统的阻抗谱在交流阻抗测试中,测试的频率范围为10mHz到100k Hz,振幅为5m V。通过测试可以得到不同频率下,阻抗的实部和虚部等信息。
3、锂离子电池的循环性能:
在25℃下,将实施例1中制备得到的电池,以1/3C恒流充电至3.8V,再以3.8V恒定电压充电至电流为0.05C,搁置5min,再以1/3C放电至2.0V,所得放电容量记为初始容量C0,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Cn,则每次循环后电池容量保持率Pn=(Cn/C0)×100%。即可用循环500次数下的电池容量保持率来体现循环性能的差异。
4、锂离子电池的倍率性能:
采用武汉金诺电子的CT-2001 A LAND电池测试系统,检测环境为室温25℃,电压范围为2.8~4.3V,分别以倍率为0.2C、0.5C、1C、2C、5C、0.2C(1C=200mAh/g-1)对所制备电极材料组装的测试电池进行5次恒流充放电循环,以第一次0.2C进行5次恒流充放电循环后的电池容量记为C1,第二次0.2C进行5次恒流充放电循环后的电池容量记为C2,倍率性能P=(C2/C1)×100%来表示。
测试结果如下表2:
表2实施例1至17及对比例1至2的性能测定

由表2可以看出,通过对比例和实施例的对比,实施例1至25,可以看到,粘结剂中包括聚丙烯酸酯类共聚物,所得到的粘结剂具备良好的粘结性能,从而适于在电池工况下充分发挥其粘结性能,进而有助于改善电池的动力学性能和安全性能,可进一步改善电池循环容量保持率。
对比例1的粘结剂中没有锂,对比例2的粘结剂粒径超过50μm,通过对比例1可以看到,粘结剂中不添加锂,粘结剂粘结力、电池的阻抗、循环性能和倍率性能均较差,通过对比例2可以看到,粘结剂粒径过大,粘结剂的循环性能和倍率性能均较差,粒径过大会导致粘结力降低,从而影响循环和倍率性能。
综上所述,本申请提出的粘结剂,所述粘结剂包括聚丙烯酸酯类共聚物和含锂化合物,使得聚合物具有很好的抗溶胀能力,并有助于发挥良好的粘结作用,提高离子电导率,控制聚合物的分子量和玻璃化转变温度,从而改善粘结剂的粘结性能。此外,粘结剂还包括含锂化合物,使粘结剂同时具有粘结剂和补锂剂两个作用,无需在锂离子电池中设置独立的金属锂层或补锂层,在锂电池中能够快速补充消耗的锂离子,增大离子传输速率,提高锂离子电池循环过程中的结构稳定性,该粘结剂涂覆在隔膜或极片上应用到锂离子电池上,提高了锂离子电池的动力学性能,降低了电化学阻抗,能够提高锂离子电池的循环性能和倍率性能。
以上仅为本发明的优选实施例,并非因此限制本发明的专利范围,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包括在本发明的专利保护范围内。

Claims (19)

  1. 一种粘结剂,其特征在于,包括聚丙烯酸酯类共聚物和含锂化合物。
  2. 如权利要求1所述的粘结剂,其特征在于,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
  3. 如权利要求2所述的粘结剂,其特征在于,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15),可选地为1:(0.05~0.7):(0.05~0.12)。
  4. 如权利要求2或3所述的粘结剂,其特征在于,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;和/或,
    所述丙烯腈类单体包括丙烯腈和甲基丙烯腈中的至少一种;和/或,
    所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种。
  5. 如权利要求1所述的粘结剂,其特征在于,所述粘结剂中,锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可选地为1:(100-600)。
  6. 如权利要求1至5任意一项所述的粘结剂,其特征在于,所述粘结剂的体积平均粒径Dv50≤50μm,可选地为7~8μm。
  7. 一种粘结剂的制备方法,其特征在于,包括:
    将聚丙烯酸酯类共聚物的单体加入第一乳化剂溶液中,得预乳化液;
    向所述预乳化液中加入引发剂进行反应,得反应液;
    向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂。
  8. 如权利要求7所述的粘结剂的制备方法,其特征在于,在步骤将聚丙烯酸酯类共聚物的单体加入第一乳化剂溶液中,得预乳化液中,所述聚丙烯酸酯类共聚物的单体包括丙烯酸酯类单体、丙烯腈类单体和丙烯酰胺类单体。
  9. 如权利要求8所述的粘结剂的制备方法,其特征在于,所述丙烯酸酯类单体、所述丙烯腈类单体和所述丙烯酰胺类单体的摩尔比为1:(0.01~0.8):(0.01~0.15),可选地为1:(0.05~0.7):(0.05~0.12)。
  10. 如权利要求8或9所述的粘结剂的制备方法,其特征在于,所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟基乙酯和甲基丙烯酸-2-羟基丙酯中的至少一种;和/或,
    所述丙烯腈类单体包括丙烯腈和甲基丙烯腈中的至少一种;和/或,
    所述丙烯酰胺类单体包括丙烯酰胺、N-羟甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺中的至少一种。
  11. 如权利要求7所述的粘结剂的制备方法,其特征在于,步骤向所述预乳化液中加入引发剂进行反应,得反应液包括:
    在加热回流条件下,将所述预乳化液加入第二乳化剂溶液中,加入引发剂反应,得反应液。
  12. 如权利要求7至11任意一项所述的粘结剂的制备方法,其特征在于,所述反应的温度为20~90℃;和/或,
    所述反应的时间为20~40min。
  13. 如权利要求7至11任意一项所述的粘结剂的制备方法,其特征在于,在步骤向所述反应液中加入含锂物质,使所述反应液的pH值为7~8,过滤得所述粘结剂中,
    所述含锂物质包括氢氧化锂、氧化锂、碳酸锂及单质锂中的至少一种;和/或,
    锂与所述聚丙烯酸酯类共聚物的质量之比为1:(10~1000),可选地为1:(100-600)。
  14. 一种隔离膜,其特征在于,包括如权利要求1至6中任一项所述的粘结剂或者通过如权利要求7至13中任一项所述的粘接剂的制备方法制得的粘接剂。
  15. 一种极片,其特征在于,包括如权利要求1至6中任一项所述的粘结剂或者通过如权利要求7至13中任一项所述的粘接剂的制备方法制得的粘接剂。
  16. 一种电极组件,其特征在于,包括如权利要求1至6中任一项所述的粘结剂、通过如权利要求7至13中任一项所述的粘接剂的制备方法制得的粘接剂、如权利要求14所述的隔离膜和如权利要求15所述的极片中的至少一种。
  17. 一种电池单体,其特征在于,包括如权利要求16所述的电极组件。
  18. 一种电池,其特征在于,包括如权利要求17所述的电池单体。
  19. 一种用电装置,其特征在于,包括如权利要求17所述的电池单体或者如权利要求18所述的电池。
PCT/CN2023/098412 2023-01-04 2023-06-05 粘结剂及其制备方法、隔离膜、极片、电极组件、电池单体、电池及用电装置 WO2024146063A1 (zh)

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JP2000195521A (ja) * 1998-12-28 2000-07-14 Nippon Zeon Co Ltd リチウムイオン二次電池電極用バインダ―組成物およびその利用
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CN111057184A (zh) * 2019-12-30 2020-04-24 宣城研一新能源科技有限公司 负极极片水性粘结剂的制备方法
CN111253534A (zh) * 2019-12-30 2020-06-09 深圳市研一新材料有限责任公司 锂离子电池用水性补锂粘结剂以及正极片的制备方法

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JP2000195521A (ja) * 1998-12-28 2000-07-14 Nippon Zeon Co Ltd リチウムイオン二次電池電極用バインダ―組成物およびその利用
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