WO2024007310A1 - 分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的装置 - Google Patents

分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的装置 Download PDF

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WO2024007310A1
WO2024007310A1 PCT/CN2022/104663 CN2022104663W WO2024007310A1 WO 2024007310 A1 WO2024007310 A1 WO 2024007310A1 CN 2022104663 W CN2022104663 W CN 2022104663W WO 2024007310 A1 WO2024007310 A1 WO 2024007310A1
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Prior art keywords
block
structural unit
dispersant
repeating structural
battery
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PCT/CN2022/104663
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English (en)
French (fr)
Inventor
卓国鹏
许云鹏
吴燕英
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 EP22936713.1A priority Critical patent/EP4325599A1/en
Priority to CN202280061793.0A priority patent/CN117981107A/zh
Priority to PCT/CN2022/104663 priority patent/WO2024007310A1/zh
Priority to US18/382,648 priority patent/US20240052244A1/en
Publication of WO2024007310A1 publication Critical patent/WO2024007310A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of battery technology, and in particular to a dispersant and its preparation method, a slurry composition and its preparation method, an electrode pole piece and a device including the electrode pole piece.
  • Batteries are widely used in electrical devices such as mobile phones, tablets, notebooks, and electric vehicles due to their high energy density, rechargeability, and good cycle performance. With the development of battery technology, higher and higher requirements have been placed on battery performance, such as cycle performance.
  • the stability of electrode slurry has a crucial impact on battery performance. Therefore, how to improve the stability of electrode slurry is an urgent problem in battery technology.
  • the present application provides a dispersant and a preparation method thereof, a slurry composition and a preparation method thereof, an electrode pole piece and an electrical device including the electrode pole piece, which can improve the stability of the slurry.
  • embodiments of the present application provide a dispersant, including a block copolymer having a first block and a second block;
  • the first block includes a first repeating structural unit represented by formula I) and formula II)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, carbonyl, carboxyl, nitro, sulfonic acid group, amide, ester group, Substituted or unsubstituted C1-C15 alkyl group, substituted or unsubstituted C1-C15 alkoxy group, substituted or unsubstituted C6-C30 aryl group;
  • the second block includes a third repeating structural unit represented by formula III) and a fourth repeating structural unit represented by formula IV):
  • the average degree of polymerization n is any integer from 1 to 25, and the dipole moments of R 8 , R 9 , and R 10 are greater than 2 ⁇ 10 -30 C ⁇ m;
  • R 8 , R 9 , and R 10 are independently selected from hydroxyl, carboxyl, pyrrolidone, ethylene oxide, propylene oxide, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C1-C15 alkoxy group, where R 9 and R 10 can be connected together to form R 9 -OR 10 or R 9 -NH-R 10 .
  • the dispersant is a block copolymer having a first block and a second block, wherein the first block includes a first repeating structural unit represented by formula I) and a block copolymer represented by formula II).
  • the above-mentioned structures can make the dispersant dissolve in the solvent, It also helps to uniformly disperse other components in the slurry, increases the solid content in the slurry, and thereby improves the stability of the slurry.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C12. Alkyl, substituted or unsubstituted C6-C12 aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, methyl, ethyl, propyl, butyl, and pentyl. , at least one of n-hexyl, phenyl and benzyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the above-mentioned groups, which can make the dispersant contribute to the composition of active materials and conductive agents.
  • the particles are evenly dispersed, and the conductivity of the slurry can also be improved, thereby reducing the resistance of the electrode piece with the slurry.
  • the first repeating structural unit has the following structural formula:
  • the second repeating structural unit is ethylene.
  • the first repeating structural unit has the above structural formula
  • the second repeating structural unit is ethylene, which can facilitate the dispersion of solid particles in the slurry.
  • the first block is a random copolymerized block of the first repeating structural unit and the second repeating structural unit.
  • the first block is a random copolymerized block of the first repeating structural unit and the second repeating structural unit, which can reduce the difficulty of preparing the dispersant.
  • the weight average molecular weight of the first block ranges from 1,000 to 500,000.
  • the weight average molecular weight of the first block is within the above range, which can help to uniformly disperse the solid particles in the slurry and increase the solid content in the slurry.
  • the weight average molecular weight of the second block is in the range of 1,000-500,000.
  • the weight average molecular weight of the second block is within the above range, which can enable the dispersant to reduce the occurrence of agglomeration of components in the slurry, and can also contribute to the uniform dispersion of each component in the slurry.
  • the average polymerization degree ratio of the first block and the second block is (0.1-10):1.
  • the average degree of polymerization of the first block and the second block is within the above range, which allows the dispersant to improve the dispersion effect of each component in the slurry and further increase the solid content in the slurry. Make the slurry have better stability.
  • the embodiments of the present application provide a method for preparing the dispersant as described in any of the above embodiments, including:
  • the monomer of the second block is added to perform the second copolymerization reaction
  • the produced product is precipitated, filtered, and dried to obtain the dispersant.
  • the preparation process is simple and safe.
  • the prepared dispersant is dissolved in the solvent, which helps to uniformly disperse other components in the slurry, increases the solid content in the slurry, and thereby improves the stability of the slurry.
  • the stirring rate is in the range of 20min/rpm-1500min/rpm.
  • the stirring rate is within the above range, which can help the initiator and the chain transfer agent to dissolve in the solvent, and facilitate the occurrence of the first copolymerization reaction and the second copolymerization reaction.
  • the reaction temperature of the first copolymerization reaction is between -20°C and 120°C.
  • the reaction temperature of the first copolymerization reaction is within the above range, which can increase the yield of the product in the first copolymerization reaction.
  • embodiments of the present application provide a slurry composition for forming an electrode film layer, including the dispersant and binder described in any of the above embodiments, active materials, and optional conductive agents. .
  • the slurry composition since the slurry composition includes the dispersant in the above embodiments, the slurry composition has a higher solid content, and the slurry formed has good stability, thereby helping to improve Battery performance.
  • the slurry composition includes, based on a total mass fraction of 100%:
  • Dispersant 0.01%-10%
  • Binder 0.5%-10%
  • rational selection of the content of each component can further improve the stability of the slurry.
  • the active material is a cathode active material.
  • the dispersant can be replaced and adsorbed on the surface of the positive active material to evenly disperse it, thereby further improving the performance of the battery.
  • the embodiments of the present application provide a method for preparing the slurry composition described in any of the above embodiments, including:
  • the pulping efficiency is improved by optimizing the feeding sequence of the components.
  • an electrode pole piece including:
  • An active material layer is provided on at least one surface of the current collector, and the active material layer is formed using the slurry composition described in any of the above embodiments.
  • the electrode piece since the active material layer of the electrode piece uses the slurry composition of the above embodiment, the electrode piece has lower resistance and can improve the cycle performance of the battery.
  • a secondary battery including:
  • the positive electrode piece and/or the negative electrode piece are the electrode pieces described in the above embodiments.
  • the battery since the positive electrode piece and/or the negative electrode piece are the electrode pieces in the above embodiment, the battery has better cycle performance.
  • embodiments of the present application provide a battery module, including the secondary battery described in the above embodiments.
  • the battery module since the secondary battery in the above embodiment is included, the battery module also has the technical effects of the above secondary battery, which will not be described again here.
  • embodiments of the present application provide a battery pack, including the secondary battery described in the above embodiment or the battery module described in the above embodiment.
  • the battery pack also has the technical effects of the above secondary battery or battery module, which will not be described again here.
  • embodiments of the present application provide an electrical device, including the secondary battery described in the above embodiment, the battery module described in the above embodiment, or the battery pack described in the above embodiment.
  • the electrical device since the secondary battery, battery module or battery pack in the above embodiment is included, the electrical device has a longer service life and cruising range.
  • Figure 1 shows a schematic structural diagram of a vehicle provided by some embodiments of the present application
  • Figure 2 shows a schematic structural diagram of a battery pack provided by some embodiments of the present application
  • Figure 3 shows a schematic diagram of the exploded structure of the battery pack in Figure 2;
  • Figure 4 shows a schematic structural diagram of the battery module in Figure 3;
  • Figure 5 shows a schematic structural diagram of a battery cell provided by some embodiments of the present application.
  • FIG. 6 shows an exploded structural diagram of the battery cell in FIG. 5 .
  • Battery pack 100 controller 200, motor 300;
  • Battery unit 30 case 31, electrode assembly 32, cover assembly 33.
  • an embodiment means that a particular feature, structure or characteristic described in connection with the embodiment can be included in at least one embodiment of the present application.
  • the appearances of this phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those skilled in the art understand, both explicitly and implicitly, that the embodiments described herein may be combined with other embodiments.
  • the terms “a” and “the” refer to one or more molecules of the compound, and are not limited to a single molecule of the compound. Furthermore, one or more molecules may or may not be identical as long as they belong to the category of chemical compounds.
  • Batteries are widely used in electrical devices such as mobile phones, tablets, notebooks, and electric vehicles due to their high energy density, rechargeability, and good cycle performance. With the development of battery technology, higher and higher requirements have been placed on battery performance, such as cycle performance.
  • the stability of electrode slurry is crucial to battery performance.
  • lipophilic dispersants such as polyvinyl alcohol, polyethylene glycol, etc.
  • the inventor found through research that the above-mentioned dispersant has limited improvement in the stability of the slurry, resulting in its poor effect on improving the performance of the battery.
  • the present application provides a dispersant and a preparation method thereof, a slurry composition and a preparation method thereof, an electrode pole piece and an electrical device including the electrode pole piece, which can improve the stability of the slurry.
  • the electrical device may be, but is not limited to, a mobile phone, a tablet, a laptop, an electric toy, an electric tool, a battery car, an electric vehicle, a ship, a spacecraft, etc.
  • electric toys can include fixed or mobile electric toys, such as game consoles, electric car toys, electric ship toys, electric airplane toys, etc.
  • spacecraft can include airplanes, rockets, space shuttles, spaceships, etc.
  • an electric device 1000 according to an embodiment of the present application is used as an example.
  • Figure 1 shows a schematic structural diagram of a vehicle provided by some embodiments of the present application.
  • the vehicle 1000 can be a fuel vehicle, a gas vehicle or a new energy vehicle.
  • the new energy vehicle can be a pure electric vehicle, a hybrid vehicle or a range-extended vehicle.
  • the battery pack 100 is disposed inside the vehicle 1000 , and the battery pack 100 may be disposed at the bottom, head, or tail of the vehicle 1000 .
  • the battery pack 100 may be used to power the vehicle 1000 , for example, the battery pack 100 may serve as an operating power source for the vehicle 1000 .
  • the vehicle 1000 may also include a controller 200 and a motor 300 .
  • the controller 200 is used to control the battery pack 100 to provide power to the motor 300 , for example, to meet the power requirements for starting, navigation, and driving of the vehicle 1000 .
  • the battery pack 100 can not only be used as an operating power source for the vehicle 1000 , but also can be used as a driving power source for the vehicle 1000 , replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000 .
  • FIG. 2 shows a schematic structural diagram of a battery pack provided by some embodiments of the present application.
  • FIG. 3 shows an exploded structural diagram of the battery pack in FIG. 2 .
  • the battery pack 100 in this application refers to including at least one battery module 20 or at least one battery cell 30 . As shown in FIGS. 2 and 3 , the battery pack 100 includes a case and a battery module 20 , and the battery module 20 is accommodated in the case.
  • the battery pack 100 includes a case and a battery module 20, and the battery module 20 is accommodated in the case.
  • the box is used to provide accommodating space for the battery module 20, and the box can adopt a variety of structures.
  • the box may include a first box 11 and a second box 12.
  • the first box 11 and the second box 12 cover each other, and the first box 11 and the second box 12 jointly define A storage space for accommodating the battery module 20 is provided.
  • the second box 12 may be a hollow structure with one end open, and the first box 11 may be a plate-like structure.
  • the first box 11 is covered with the open side of the second box 12 so that the first box 11 and the second box 11 are connected to each other.
  • the two boxes 12 jointly define an accommodation space; the first box 11 and the second box 12 can also be hollow structures with one side open, and the open side of the first box 11 is covered with the second box 12 Open side.
  • the box formed by the first box 11 and the second box 12 can be in various shapes, such as cylinder, rectangular parallelepiped, etc.
  • the battery pack 100 there may be multiple battery modules 20, and the multiple battery modules 20 may be connected in series, in parallel, or in mixed connection.
  • Mixed connection means that the multiple battery modules 20 are connected in series and in parallel.
  • Multiple battery modules 20 can be directly connected in series, parallel, or mixed together, and then the entire battery module 20 is accommodated in the box.
  • FIG. 4 shows a schematic structural diagram of the battery module in FIG. 3 .
  • the battery module 20 includes one or more battery cells 30 .
  • the battery module 20 includes a plurality of battery cells 30 , and the plurality of battery cells 30 can be connected in series, in parallel, or in a mixed connection.
  • a mixed connection means that the plurality of battery cells 30 have both series and There is parallel connection.
  • Multiple battery cells 30 can be directly connected in series or in parallel or mixed together.
  • Each battery cell 30 may be a secondary battery cell or a primary battery; it may also be a lithium-ion battery, a sodium-ion battery, a magnesium-ion battery, or a potassium-ion battery, but is not limited thereto.
  • the battery cell 30 may be in the shape of a cylinder, a flat body, a rectangular parallelepiped or other shapes.
  • FIG. 5 shows a schematic structural diagram of a battery cell provided by some embodiments of the present application.
  • FIG. 6 shows an exploded structural diagram of the battery cell in FIG. 5 .
  • the battery cell 30 refers to the smallest unit that constitutes the battery.
  • the battery cell 30 includes a case 31 , an electrode assembly 32 and a cover assembly 33 .
  • the housing 31 has a chamber for accommodating the electrode assembly 32 , and the cover assembly 33 is used to close the opening of the housing 31 .
  • the cover assembly 33 includes an end cover, and the end cover is connected with the case 31 to form a shell of the battery cell 30 .
  • the electrode assembly 32 is disposed in the case 31 , and the case 31 is filled with electrolyte.
  • the end cap refers to a component that covers the opening of the case 31 to isolate the internal environment of the battery cell 30 from the external environment.
  • the shape of the end cap can be adapted to the shape of the housing 31 to fit the housing 31 .
  • the end cap can be made of a material with a certain hardness and strength (such as aluminum alloy). In this way, the end cap is less likely to deform when subjected to extrusion and collision, allowing the battery cell 30 to have higher structural strength. , the safety performance can also be improved.
  • Functional components such as electrode terminals can be provided on the end cap. The electrode terminals may be used to electrically connect with the electrode assembly 32 for outputting or inputting electrical energy from the battery cell 30 .
  • the end cap may also be provided with a pressure relief mechanism for releasing the internal pressure when the internal pressure or temperature of the battery cell 30 reaches a threshold value.
  • the end cap can also be made of various materials, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which are not particularly limited in the embodiments of the present application.
  • an insulating member may also be provided inside the end cover, and the insulating member may be used to isolate the electrical connection components in the housing 31 from the end cover to reduce the risk of short circuit.
  • the insulating member may be plastic, rubber, etc.
  • the housing 31 is a component used to cooperate with the end cap to form an internal environment of the battery cell 30, wherein the internal environment formed can be used to accommodate the electrode assembly 32, electrolyte and other components.
  • the casing 31 and the end cover may be independent components, and an opening may be provided on the casing 31.
  • the end cover covers the opening at the opening to form the internal environment of the battery cell 30.
  • the end cover and the housing 31 can also be integrated.
  • the end cover and the housing 31 can form a common connection surface before other components are put into the housing. When it is necessary to encapsulate the inside of the housing 31, Then the end cap is closed with the housing 31 .
  • the housing 31 can be of various shapes and sizes, such as rectangular parallelepiped, cylinder, hexagonal prism, etc.
  • the electrode assembly 32 is a component in the battery cell 30 where electrochemical reactions occur.
  • One or more electrode assemblies 32 may be contained within the housing 31 .
  • the electrode assembly 32 is mainly formed by winding or stacking a positive electrode piece and a negative electrode piece, and usually a separator is provided between the positive electrode piece and the negative electrode piece.
  • the portions of the positive electrode tab and the negative electrode tab that contain active material constitute the main body of the electrode assembly 32 , and the portions of the positive electrode tab and the negative electrode tab that do not contain active material each constitute tabs.
  • the positive electrode tab and the negative electrode tab can be located together at one end of the main body or respectively located at both ends of the main body. During the charging and discharging process of the battery, the positive active material and negative active material react with the electrolyte, and the tabs are connected to the electrode terminals to form a current loop.
  • the embodiments of the present application provide a dispersant, which includes a block copolymer having a first block and a second block, wherein the first block includes a first repeating structural unit represented by formula I) and the second repeating structural unit represented by formula II):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, carbonyl, carboxyl, nitro, sulfonic acid group, amide, ester group, Substituted or unsubstituted C1-C15 alkyl group, substituted or unsubstituted C1-C15 alkoxy group, substituted or unsubstituted C6-C30 aryl group;
  • the second block includes a third repeating structural unit represented by formula III) and a fourth repeating structural unit represented by formula IV):
  • the average degree of polymerization n is any integer from 1 to 25, and the dipole moments of R 8 , R 9 , and R 10 are greater than 2 ⁇ 10 -30 C ⁇ m.
  • halogen refers to fluorine, chlorine, bromine or iodine.
  • substituted when a compound or chemical structural feature (eg, alkyl, aryl) is said to be "substituted,” that feature may have one or more substituents.
  • substituted has the broadest meaning known to those of ordinary skill in the art and includes a moiety that occupies the space normally occupied by one or more hydrogen atoms associated with the parent compound or chemical structural feature. Location.
  • C1-C15 alkyl refers to a linear or branched chain alkyl group with 1 to 15 carbon atoms.
  • alkyl groups include but are not limited to methyl, ethyl, n-propyl, isopropyl, etc.
  • C6-C30 aryl refers to a closed aromatic ring or ring system having 6 to 30 carbon atoms.
  • aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, anthracenyl, biphenyl (including diphenyl, terphenyl), triphenylene, pyrenyl, spirobifluorenyl, base, perylene group, indenyl group, azulenyl group, and benzophenanthyl group.
  • sterically hindered group refers to any functional group capable of causing mutual repulsion in a spatial arrangement.
  • the sterically hindered group includes, but is not limited to, hydroxyl, alkoxy, and cycloalkoxy.
  • C1-C15 alkoxy refers to a linear or branched C1-C15 alkyl group, or a cycloalkyl group having 1 to 15 carbon atoms, where in each case There are one or more oxygen atoms between two carbon atoms.
  • Alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy , heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, ethylene oxide Alkyl, propylene oxide, hexyl oxide, octyl oxide.
  • the dispersant is a block copolymer having a first block and a second block, wherein the first block includes a first repeating structural unit represented by formula I) and a block copolymer represented by formula II).
  • the second repeating structural unit, the second block includes a third repeating structural unit represented by formula III) and a fourth repeating structural unit represented by formula IV).
  • the above-mentioned structures can make the dispersant dissolve in the solvent, and It helps to uniformly disperse other components in the slurry, increases the solid content in the slurry, and thereby improves the stability of the slurry.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkane. group, substituted or unsubstituted C6-C12 aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the above groups, which can make the dispersant quickly dissolve in the organic solvent and be adsorbed on the
  • the surface of the solid particles in the slurry can help the uniform dispersion of the solid particles and further increase the solid content in the slurry.
  • the uniform dispersion of each component in the slurry can also improve the conductivity of the slurry to reduce the resistance of the electrode piece with the slurry.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, methyl, ethyl, propyl , at least one of butyl, pentyl, n-hexyl, phenyl and benzyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, cyano, methyl, ethyl, propyl, butyl. At least one of , pentyl, n-hexyl, phenyl and benzyl groups helps to further increase the solid content in the slurry and reduce the resistance of the electrode pole piece with the slurry.
  • the first repeating structural unit has the structural formula of formula V):
  • the second repeating structural unit is ethylene.
  • the first repeating structural unit has the above structural formula
  • the second repeating structural unit is ethylene, which can help the dispersant to be firmly adsorbed on the surface of the solid particles in the slurry, so that the solid particles are evenly dispersed.
  • the first block is a random copolymerized block of a first repeating structural unit and a second repeating structural unit.
  • the first block is a random copolymerized block of the first repeating structural unit and the second repeating structural unit, which can reduce the difficulty of preparing the dispersant.
  • the weight average molecular weight of the first block ranges from 1,000 to 500,000.
  • the weight average molecular weight of the first block is within the above range, which can help to uniformly disperse the solid particles in the slurry and increase the solid content in the slurry.
  • the weight average molecular weight of the first block may be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000 or higher.
  • the second block includes a third repeating structural unit represented by formula III) and a fourth repeating structural unit represented by formula IV), wherein the third repeating structural unit represented by formula III)
  • the structural unit can be used as a steric hindrance group, and can be randomly copolymerized with the fourth repeating structural unit shown in formula IV) to form a random copolymer block. This can provide greater steric hindrance between dispersant molecules and reduce The occurrence of agglomeration of components in the slurry.
  • R 8 is selected from hydroxyl, carboxyl, pyrrolidone, ethylene oxide, propylene oxide, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C1-C15 of alkoxy.
  • R 8 is selected from the above-mentioned groups to provide greater steric hindrance between dispersant molecules and reduce the occurrence of agglomeration of components in the slurry.
  • R 9 and R 10 are independently selected from hydroxyl, carboxyl, pyrrolidone, ethylene oxide, propylene oxide, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or Unsubstituted C1-C15 alkoxy group, wherein R 9 and R 10 can be connected together to form R 9 -OR 10 or R 9 -NH-R 10 .
  • R 9 and R 10 are selected from the above groups, which can not only provide greater steric hindrance between the dispersant molecules, but also enable the dispersant to help improve the various components in the slurry. dispersion effect.
  • the weight average molecular weight of the second block ranges from 1,000 to 500,000.
  • the weight average molecular weight of the second block is within the above range, which can enable the dispersant to reduce the occurrence of agglomeration of components in the slurry, and can also contribute to the uniform dispersion of each component in the slurry.
  • the weight average molecular weight of the second block may be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000 or higher.
  • the average polymerization degree ratio of the first block and the second block is (0.1-10):1.
  • the average degree of polymerization of the first block and the second block is within the above range, which can improve the dispersion effect of each component in the slurry and further increase the solid content in the slurry, making the slurry Has better stability.
  • the embodiments of the present application provide a method for preparing the dispersant in any of the above embodiments, including:
  • the preparation process is simple and safe.
  • the prepared dispersant is dissolved in the solvent, which helps to uniformly disperse other components in the slurry, increases the solid content in the slurry, and thereby improves the stability of the slurry.
  • the stirring rate in step S10 is in the range of 20 min/rpm-1500 min/rpm.
  • the stirring linear speed is within the above range, which can help the initiator and the chain transfer agent dissolve in the solvent, which is beneficial to the occurrence of the first copolymerization reaction and the second copolymerization reaction.
  • the reaction temperature of the first copolymerization reaction in step S20 is between -20°C and 120°C.
  • the reaction temperature of the first copolymerization reaction is within the above range, which can increase the yield of the product in the first copolymerization reaction.
  • the initiator may be any one or more initiators used in copolymerization reactions, such as azo compounds.
  • the initiator can be, but is not limited to, azobisisobutyronitrile (AIBN for short).
  • the chain transfer agent can be any one or more chain transfer agents used in copolymerization reactions, and the embodiments of the present application do not specifically limit this.
  • the chain transfer agent may have the structural formula of formula VI):
  • R 11 is selected from C1-C5 alkyl group.
  • the embodiments of the present application provide a slurry composition for forming an electrode film layer, including the dispersant in any of the above embodiments as well as a binder, active material and optional conductive agent.
  • the slurry composition since the slurry composition includes the dispersant in the above embodiments, the slurry composition has a higher solid content, and the slurry formed has good stability, thereby helping to improve Battery performance.
  • the binder may include, but is not limited to, sodium polyacrylate, polyacrylamide, polyacrylic acid, polyacrylate, polyacrylonitrile, styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, At least one type of polyvinyl alcohol.
  • the conductive agent may include, but is not limited to, at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the slurry composition includes, based on a total mass fraction of 100%:
  • Dispersant 0.01%-10%
  • Binder 0.5%-10%
  • rational selection of the content of each component can further improve the stability of the slurry.
  • the active material is a cathode active material
  • the cathode active material may be any one or more cathode active materials used in batteries.
  • the cathode active material may include at least one of the following materials: lithium-containing phosphates with an olivine structure, lithium transition metal oxides, 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 (abbreviated as NCM333), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (abbreviated as NCM523), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (abbreviated as NCM211), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (abbreviated as NCM622), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (abbreviated as NCM811) , at least one of lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O 2 ) and
  • lithium-containing phosphates with an olivine structure may include but are not limited to lithium iron phosphate (such as LiFePO (can also be referred to as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), composite materials of lithium manganese phosphate and carbon, lithium iron manganese phosphate, composite materials of lithium manganese iron phosphate and carbon at least one of the materials.
  • lithium iron phosphate such as LiFePO (can also be referred to as LFP)
  • composite materials of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate
  • composite materials of lithium manganese phosphate and carbon at least one of the materials.
  • the active material may also be a negative active material, and the negative active material may be any one or more negative active materials used in 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 dispersant can be replaced and adsorbed on the surface of the positive active material to evenly disperse it, thereby further improving the performance of the battery.
  • the embodiments of the present application provide a method for preparing a slurry composition, including:
  • the pulping efficiency is improved by optimizing the feeding sequence of the components.
  • the stirring linear speed and stirring time of the slurry can be reduced.
  • the linear speed of stirring in step S50 is 2m/s-10m/s, and the stirring time is 5min-40min;
  • the linear speed of stirring in step S60 is 2m/s-10m/s, and the stirring time is 5min-40min;
  • the stirring linear speed in step S70 is 2m/s-10m/s, and the stirring time is 150min-220min.
  • the embodiments of the present application provide an electrode plate, including a current collector and an active material layer, wherein the active material layer is provided on at least one surface of the current collector, and the active material layer uses the slurry composition in any of the above embodiments. form.
  • the electrode piece since the active material layer of the electrode piece uses the slurry composition of the above embodiment, the electrode piece has lower resistance and can improve the cycle performance of the battery.
  • the 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
  • Embodiments of the present application provide a secondary battery, including a positive electrode plate, a negative electrode plate and a separator.
  • the separator is located between the positive electrode piece and the negative electrode piece.
  • the positive electrode piece and/or the negative electrode piece are the electrode pieces in the above embodiments.
  • the battery since the positive electrode piece and/or the negative electrode piece are the electrode pieces in the above embodiment, the battery has better cycle performance.
  • the positive electrode piece is the electrode piece in the above embodiment, and the active material layer is the positive active material layer.
  • the positive electrode sheet can be prepared by the following method: coating the above-mentioned positive electrode slurry composition on at least one surface of the positive electrode current collector, drying, and cold pressing to obtain the positive electrode sheet.
  • the negative electrode piece is the electrode piece in the above embodiment, and the active material layer is the negative active material layer.
  • the negative electrode sheet can be prepared by the following method: coating the above-mentioned negative electrode slurry composition on at least one surface of the negative electrode current collector, drying, and cold pressing to obtain the negative electrode sheet.
  • the material of the separator can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, and is not particularly limited.
  • the materials of each layer can be the same or different, and are not particularly limited.
  • an electrolyte is also included, and the electrolyte plays a role in conducting ions between the positive electrode piece and the negative electrode piece.
  • 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, At least one of lithium triflate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate and lithium tetrafluoroxalate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethyl carbonate.
  • the electrolyte solution optionally further includes additives.
  • 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 above-mentioned positive electrode pieces, separators, and negative electrode pieces are stacked in order, so that the separator plays an isolation role between the positive electrode pieces and the negative electrode pieces, and an electrode assembly is obtained, or the electrode assembly can be obtained after winding;
  • the electrode assembly is connected to the tab, and the electrode assembly is placed in the packaging shell, and then heated to remove excess water, and then the electrolyte is injected and sealed; finally, after standing, hot and cold pressing, formation, shaping, capacity testing and other processes, the result is Secondary battery of the present application.
  • An embodiment of the present application provides a battery module, including the secondary battery in the above embodiment. Since it includes the secondary battery in the above embodiment, the battery module also has the technical effects of the above-mentioned secondary battery, which will not be described again here.
  • the embodiment of the present application provides a battery pack, including the secondary battery in the above embodiment or the battery module described in the above embodiment. Since the battery pack includes the secondary battery or battery module in the above embodiment, the battery pack also has the technical effects of the above-mentioned secondary battery or battery module, which will not be described again here.
  • Embodiments of the present application provide an electrical device, including the secondary battery in the above embodiment, the battery module in the above embodiment, or the battery pack in the above embodiment. Since it includes the secondary battery, battery module or battery pack in the above embodiment, the electrical device has a longer service life and cruising range.
  • the specific preparation steps of the positive electrode sheet are as follows:
  • the weight ratio of the above-mentioned lithium iron phosphate, carbon nanotubes, PVDF and dispersant is 91.9:5:3:0.1.
  • the specific preparation steps of the negative electrode piece are as follows:
  • Example 17 The preparation method of the secondary batteries of Examples 2-26 and Comparative Example 1 is similar to that of Example 1, and the differences are listed in Table 1 respectively.
  • the first repeating structural unit has the formula (A)
  • the second repeating structural unit has the structural formula of formula (B)
  • the fourth repeating structural unit has the structural formula of formula (C).
  • the first repeating structural unit has the structural formula of formula (D)
  • the second repeating structural unit has the structural formula of formula (E)
  • the fourth repeating structural unit has the structural formula of formula (F).
  • the first repeating structural unit has the structural formula of formula (H)
  • the second repeating structural unit has the structural formula of formula (M)
  • the fourth repeating structural unit has the structural formula of formula (G).
  • the positive electrode slurry is coated on the aluminum foil and dried to obtain the positive electrode sheet.
  • the calculation formula for the solid content W of the positive electrode slurry is as follows:
  • m 0 is the mass of the aluminum foil
  • m 1 is the mass of the dried positive electrode piece
  • m 2 is the mass of the wet positive electrode piece obtained after coating the aluminum foil with the positive electrode slurry.
  • T total represents the total stirring time for the formation of the positive electrode slurry composition, the unit is min;
  • W represents the solid content in the slurry, in %
  • Z represents the resistivity of the positive electrode piece, the unit is ⁇ .cm
  • K represents the capacity retention rate of the battery after 1000 cycles at 25°C, in %.
  • the dispersant provided in the embodiment of the present application can increase the solid content in the slurry and make the slurry have better stability. And the slurry can make the electrode pole piece have lower resistance, and also make the battery have better capacity retention rate and cycle performance.

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Abstract

本申请提供了一种分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的用电装置，分散剂包括具有第一嵌段和第二嵌段的嵌段共聚物，第一嵌段包括式Ⅰ)所示的第一重复结构单元和式Ⅱ)所示的第二重复结构单元，第二嵌段包括式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元，其中，n为1-25中的任意一个整数，R 1-R 7分别独立地选自氢、卤素、氰基、羰基、羧基、硝基、磺酸基、酰胺、酯基、取代或未取代的C1-C15的烷基及烷氧基、取代或未取代的C6-C30的芳基，R 8、R 9、R 10的偶极矩大于2×10 -30C·m。分散剂能够提高浆料的稳定性。

Description

分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的装置 技术领域
本申请涉及电池技术领域，特别是涉及一种分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的装置。
背景技术
电池由于具有能量密度高、可充电、循环性能好等优点，被广泛应用于手机、平板电脑、笔记本、电动车辆等用电装置中。随着电池技术的发展，对电池的性能提出了越来越高的要求，例如循环性能等。
而电极浆料的稳定性对电池性能的影响是至关重要的，因此，如何提高电极浆料的稳定性，是电池技术中一个亟待解决的问题。
发明内容
本申请提供了一种分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的用电装置，能够提高浆料的稳定性。
第一方面，本申请实施例提供了一种分散剂，包括具有第一嵌段和第二嵌段的嵌段共聚物；
所述第一嵌段包括具有式Ⅰ)所示的第一重复结构单元和式Ⅱ)
所示的第二重复结构单元：
Figure PCTCN2022104663-appb-000001
其中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、羰基、羧基、硝基、磺酸基、酰胺、酯基、取代或未取代的C1-C15的烷基、取代或未取代的C1-C15的烷氧基、取代或未取代的C6-C30的芳基；
所述第二嵌段包括具有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元：
Figure PCTCN2022104663-appb-000002
其中，平均聚合度n为1-25中的任意一个整数，R 8、R 9、R 10的偶极矩大于2×10 -30C·m；
可选地，R 8、R 9、R 10分别独立地选自羟基、羧基、吡咯烷酮、环氧乙烷、环氧丙烷、卤素、取代或未取代的C1-C15的烷基、取代或未取代的C1-C15的烷氧基，其中，R 9和R 10可连接在一起为R 9-O-R 10或R 9-NH-R 10。
在上述实施例中，分散剂具有第一嵌段和第二嵌段的嵌段共聚物，其中，第一嵌段包括具有式Ⅰ)所示的第一重复结构单元和式Ⅱ)所示的第二重复结构单元，第二嵌段包括具有式有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元，上述这些结构能够使分散剂溶于溶剂中，并有助于浆料中其它组分的均匀分散，增加浆料中的固含量，从而提高浆料的稳定性。
在申请请的一些实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、取代或未取代的C1-C12的烷基、取代或未取代的C6-C12的芳基。可选地，R 1、R 2、R 3、R 4、R 5、R 6和R 7分 别独立地选自氢、卤素、氰基、甲基、乙基、丙基、丁基、戊基、正己、苯基和苄基中的至少一种。
在上述这些实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自上述基团，可使分散剂有助于活性材料及导电剂等组分的均匀分散，并且还能够提高浆料的导电性，从而降低具有该浆料的电极极片的电阻。
在本申请的一些实施例中，所述第一重复结构单元具有如下结构式：
Figure PCTCN2022104663-appb-000003
所述第二重复结构单元为乙烯。
在上述这些实施例中，第一重复结构单元具有上述结构式，以及第二重复结构单元为乙烯，可有助于浆料中固体颗粒的分散。
在本申请的一些实施例中，所述第一嵌段为所述第一重复结构单元和所述第二重复结构单元的无规共聚嵌段。
在上述这些实施例中，第一嵌段为第一重复结构单元和第二重复结构单元的无规共聚嵌段，这样可降低分散剂的制备难度。
在本申请的一些实施例中，所述第一嵌段的重均分子量在1000-500000范围内。
在上述这些实施例中，第一嵌段的重均分子量在上述范围内，可有助于浆料中固体颗粒的均匀分散，提高浆料中的固含量。
在本申请的一些实施例中，所述第二嵌段的重均分子量在1000-500000范围内。
在上述这些实施例中，第二嵌段的重均分子量在上述范围内，可使分散剂减少浆料中组分团聚的发生，还可有助于浆料中各组分的均匀分散。
在本申请的一些实施例中，所述第一嵌段和第二嵌段物的平均聚合度比为(0.1-10)：1。
在上述这些实施例中，第一嵌段和第二嵌段的平均聚合度在上述范围内，可使分散剂提高浆料中各组分的分散效果，并进一步提高浆料中的固含量，使浆料具有较好的稳定性。
第二方面，本申请实施例提供了一种如上述任一项实施例中所述分散剂的制备方法，包括：
将引发剂、链转移剂溶解于有机溶剂中，并于惰性氛围下搅拌，得到混合溶液；
向所述混合溶液内添加第一嵌段的单体进行第一共聚反应；
待第一共聚反应完成后，再添加第二嵌段的单体进行第二共聚反应；
待第二共聚反应完成后，所产生的产物经沉淀、过滤、干燥，得到所述分散剂。
在上述实施例中，制备工艺简单，且制备安全。所制备得到的分散剂溶于溶剂中，有助于浆料中其它组分的均匀分散，增加浆料中的固含量，从而提高浆料的稳定性。
在本申请的一些实施例中，所述搅拌的速率在20min/rpm-1500min/rpm范围内。
在上述这些实施例中，搅拌速率在上述范围内，可有助于引发剂和链转移剂溶解于溶剂中，利于第一共聚反应和第二共聚反应的发生。
在本申请的一些实施例中，第一共聚反应的反应温度在-20℃-120℃。
在上述这些实施例中，第一共聚反应的反应温度在上述范围内，可提高第一共聚反应中产物的产率。
第三方面，本申请实施例提供了一种用于形成电极膜层的浆料组合物，包括上述任一项实施例中所述的分散剂以及粘结剂、活性材料和任选的导电剂。
在上述实施例中，浆料组合物由于包括上述实施例中的分散剂，因此，该浆料组合物具有较高的固含量，进而形成的浆料具有良好的稳定性，从而有助于提高电池的性能。
在本申请的一些实施例中，所述浆料组合物按总质量分数为100％计包含:
分散剂，0.01％-10％；
粘结剂，0.5％-10％；
活性材料，82％-91.99％；
导电剂，0％-15％。
在上述这些实施例中，合理选择各组分的含量，能够进一步提高浆料的稳定性。
在本申请的一些实施例中，所述活性材料为正极活性材料。
在上述实施例中，分散剂能够更换吸附于正极活性材料表面，使其均匀分散，从而可以进一步提高电池的性能。
第四方面，本申请实施例提供了一种上述任一项实施例中所述的浆料组合物的制备方法，包括：
将导电剂、分散剂和部分溶剂在搅拌条件下混合，得到第一混合物；
将粘结剂添加至所述第一混合物进行搅拌混合，得到第二混合物；
将活性材料和余量溶剂添加至所述第二混合物进行搅拌混合，得到所述浆料组合物。
在上述这些实施例中，通过优化组分的加料顺序，提高制浆效率。
第五方面，本申请实施例提供了一种电极极片，包括：
集流体；
活性材料层，设于所述集流体的至少一个表面，所述活性材料层使用上述任一项实施例中所述的浆料组合物形成。
在上述实施例中，由于电极极片的活性材料层使用上述实施例的浆料组合物，因此，该电极极片具有较低的电阻，并且能够提高电池的循环性能。
第六方面，本申请实施例提供了一种二次电池，包括：
正极极片；
负极极片；
隔膜，设于所述正极极片和所述负极极片之间；
其中，所述正极极片和/或所述负极极片为上述实施例中所述的电极极片。
在上述实施例中，由于正极极片和/或负极极片为上述实施例中的电极极片，因此，该电池具有较好的循环性能。
第七方面，本申请实施例提供了一种电池模块，包括上述实施例中所述的二次电池。
在上述实施例中，由于包括了上述实施例中的二次电池，因此，该电池模块也具有上述二次电池所具有的技术效果，在此不做赘述。
第八方面，本申请实施例提供了一种电池包，包括上述实施例中所述的二次电池或上述实施例中所述的电池模块。
在上述实施例中，由于包括了上述实施例中的二次电池或电池模块，因此，该电池包也具有上述二次电池或电池模块所具有的技术效果，在此不做赘述。
第九方面，本申请实施例提供了一种用电装置，包括上述实施例中所述的二次电池、上述实施例中所述的电池模块或上述实施例中所述的电池包。
在上述实施例中，由于包括了上述实施例中的二次电池、电池模块或电池包，因此，该用电装置具有较长的使用寿命及续航里程。
附图说明
为了更清楚地说明本申请实施例，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，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，还可以根据附图获得其他的附图。
图1示出了本申请一些实施例提供的车辆的结构示意图；
图2示出了本申请一些实施例提供的电池包的结构示意图；
图3示出了图2中电池包的分解结构示意图；
图4示出了图3中电池模块的结构示意图；
图5示出了本申请一些实施例提供的电池单体的结构示意图；
图6示出了图5中电池单体的分解结构示意图。
在附图中，附图并未按照实际的比例绘制。
标记说明：
车辆1000；
电池包100，控制器200，马达300；
第一箱体11，第二箱体12；
电池模块20；
电池单体30，壳体31，电极组件32，盖体组件33。
具体实施方式
下面将结合附图对本申请的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本申请，因此只作为示例，而不能以此来限制本申请的保护范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请的说明书和权利要求书及上述附图说明中的术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的包含。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
在本申请实施例的的描述中，除非另有说明，“以上”、“以下”为包含本数，“一种或多种”、“一个或多个”中“多种”、“多个”的含义是两种(个)以上。
在本申请实施例的的描述中，术语“一种”、“该”均是指该化合物的一个或多个分子，而不是限于该化合物的单个分子。此外，一个或多个分子可以相同或可以不相同，只要它们属于该化学化合物的范畴即可。
本文公开的替换性要素或实施方式的分组不应被理解为限制。每个组成员可被单独采用和被单独要求保护，或者与该组其它成员或在本文中找到的其它要素以任何组合被采用和要求保护。可以预见到，为了方便和/或可专利性的理由，组中的一个或多个成员可被包含进组中或从中删除。当任何此类包含或删除发生时，说明书在此被看作为含有经过改动的组，因此满足对权利要求书中所用的全部马库什组的书面描述。
在不脱离本申请的保护范围的情况下，在本申请中能进行各种修改和变化，这对于本领域技术人员来说是显而易见的。因而，本申请意在覆盖落入所对应权利要求(要求保护的范围)及其等同范围内的本申请的修改和变化。需要说明的是，本申请实施例所提供的实施方式，在不矛盾的情况下可以相互组合。
在阐述本申请实施例所提供的保护范围之前，为了便于对本申请实施例理解，本申请首先对相关技术中存在的问题进行具体说明。
电池由于具有能量密度高、可充电、循环性能好等优点，被广泛应用于手机、平板电脑、笔记本、电动车辆等用电装置中。随着电池技术的发展，对电池的性能提出了越来越高的要求，例如循环性能等。
电极浆料的稳定性对电池性能的影响是至关重要的。目前，浆 料中通常会添加亲油的分散剂，例如聚乙烯醇、聚乙二醇等，以提高浆料中固体组分在有机溶剂中的分散效果，从而实现提高浆料的稳定性的目的。发明人经研究发现，上述分散剂对浆料的稳定性的提高有限，从而导致其对电池的性能提升的效果不佳。
鉴于此，本申请提供了一种分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的用电装置，能够提高浆料的稳定性。
在本申请中，用电装置可以为但不限于手机、平板、笔记本电脑、电动玩具、电动工具、电瓶车、电动汽车、轮船、航天器等等。其中，电动玩具可以包括固定式或移动式的电动玩具，例如，游戏机、电动汽车玩具、电动轮船玩具和电动飞机玩具等等，航天器可以包括飞机、火箭、航天飞机和宇宙飞船等等。
以下实施例为了方便说明，以本申请一实施例的一种用电装置为车辆1000为例进行说明。
图1示出了本申请一些实施例提供的车辆的结构示意图。
如图1，车辆1000可以为燃油汽车、燃气汽车或新能源汽车，新能源汽车可以是纯电动汽车、混合动力汽车或增程式汽车等。车辆1000的内部设置有电池包100，电池包100可以设置在车辆1000的底部或头部或尾部。电池包100可以用于车辆1000的供电，例如，电池包100可以作为车辆1000的操作电源。车辆1000还可以包括控制器200和马达300，控制器200用来控制电池包100为马达300供电，例如，用于车辆1000的启动、导航和行驶时的工作用电需求。
在本申请的一些实施例中，电池包100不仅可以作为车辆1000的操作电源，还可以作为车辆1000的驱动电源，代替或部分地代替燃油或天然气为车辆1000提供驱动动力。
图2示出了本申请一些实施例提供的电池包的结构示意图。图3示出了图2中电池包的分解结构示意图。
本申请中的电池包100是指包括至少一个电池模块20或至少一个电池单体30。如图2和图3，电池包100包括箱体和电池模块20，电池模块20容纳于箱体内。
电池包100包括箱体和电池模块20，电池模块20容纳于箱体内。其中，箱体用于为电池模块20提供容纳空间，箱体可以采用多种结构。在一些实施例中，箱体可以包括第一箱体11和第二箱体12，第一箱体11与第二箱体12相互盖合，第一箱体11和第二箱体12共同限定出用于容纳电池模块20的容纳空间。第二箱体12可以为一端开口的空心结构，第一箱体11可以为板状结构，第一箱体11盖合于第二箱体12的开口侧，以使第一箱体11与第二箱体12共同限定出容纳空间；第一箱体11和第二箱体12也可以是均为一侧开口的空心结构，第一箱体11的开口侧盖合于第二箱体12的开口侧。当然，第一箱体11和第二箱体12形成的箱体可以是多种形状，比如，圆柱体、长方体等。
在电池包100中，电池模块20可以是多个，多个电池模块20之间可串联或并联或混联，混联是指多个电池模块20中既有串联又有并联。多个电池模块20之间可直接串联或并联或混联在一起，再将多个电池模块20构成的整体容纳于箱体内。
图4示出了图3中电池模块的结构示意图。
电池模块20包括一个或多个电池单体30。例如，如图4所示，电池模块20包括多个电池单体30，多个电池单体30之间可串联或并联或混联，混联是指多个电池单体30中既有串联又有并联。多个电池单体30之间可直接串联或并联或混联在一起。
其中，每个电池单体30可以为二次电池单体或一次电池；还可以是锂离子电池、钠离子电池、镁离子电池、钾离子电池，但不局限于此。电池单体30可呈圆柱体、扁平体、长方体或其它形状等。
图5示出了本申请一些实施例提供的电池单体的结构示意图。图6示出了图5中电池单体的分解结构示意图。
如5所示，电池单体30是指组成电池的最小单元。如图6所示，电池单体30包括壳体31、电极组件32和盖体组件33。壳体31具有容纳电极组件32的腔室，盖体组件33用于封闭壳体31的开口。盖体组件33包括端盖，端盖与壳体31连接形成电池单体30的外壳，电极组件32设在壳体31内，且壳体31内填充电解质。
端盖是指盖合于壳体31的开口处以将电池单体30的内部环境隔绝于外部环境的部件。不限地，端盖的形状可以与壳体31的形状相适应以配合壳体31。可选地，端盖可以由具有一定硬度和强度的材质(如铝合金)制成，这样，端盖在受挤压碰撞时就不易发生形变，使电池单体30能够具备更高的结构强度，安全性能也可以有所提高。端盖上可以设置有如电极端子等的功能性部件。电极端子可以用于与电极组件32电连接，以用于输出或输入电池单体30的电能。在一些实施例中，端盖上还可以设置有用于在电池单体30的内部压力或温度达到阈值时泄放内部压力的泄压机构。端盖的材质也可以是多种的，比如，铜、铁、铝、不锈钢、铝合金、塑胶等，本申请实施例对此不作特殊限制。在一些实施例中，在端盖的内侧还可以设置有绝缘件，绝缘件可以用于隔离壳体31内的电连接部件与端盖，以降低短路的风险。示例性的，绝缘件可以是塑料、橡胶等。
壳体31是用于配合端盖以形成电池单体30的内部环境的组件，其中，形成的内部环境可以用于容纳电极组件32、电解质以及其他 部件。壳体31和端盖可以是独立的部件，可以于壳体31上设置开口，通过在开口处使端盖盖合开口以形成电池单体30的内部环境。不限地，也可以使端盖和壳体31一体化，具体地，端盖和壳体31可以在其他部件入壳前先形成一个共同的连接面，当需要封装壳体31的内部时，再使端盖盖合壳体31。壳体31可以是多种形状和多种尺寸的，例如长方体形、圆柱体形、六棱柱形等。
电极组件32是电池单体30中发生电化学反应的部件。壳体31内可以包含一个或更多个电极组件32。电极组件32主要由正极极片和负极极片卷绕或层叠放置形成，并且通常在正极极片与负极极片之间设有隔膜。正极极片和负极极片具有活性物质的部分构成电极组件32的主体部，正极极片和负极极片不具有活性物质的部分各自构成极耳。正极极耳和负极极耳可以共同位于主体部的一端或是分别位于主体部的两端。在电池的充放电过程中，正极活性物质和负极活性物质与电解质发生反应，极耳连接电极端子以形成电流回路。
用于二次电池的分散剂
本申请实施例提供了一种分散剂，该分散剂包括具有第一嵌段和第二嵌段的嵌段共聚物，其中，第一嵌段包括具有式Ⅰ)所示的第一重复结构单元和式Ⅱ)所示的第二重复结构单元：
Figure PCTCN2022104663-appb-000004
其中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、羰基、羧基、硝基、磺酸基、酰胺、酯基、取代或未取代的 C1-C15的烷基、取代或未取代的C1-C15的烷氧基、取代或未取代的C6-C30的芳基；
第二嵌段包括具有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元：
Figure PCTCN2022104663-appb-000005
其中，平均聚合度n为1-25中的任意一个整数，R 8、R 9、R 10的偶极矩大于2×10 -30C·m。
在本申请中，卤素是指氟、氯、溴或碘。
在本申请中，当化合物或化学结构特征(例如烷基、芳基)被称为是“取代的”时，该特征可具有一个或多个取代基。术语“取代基”具有本领域普通技术人员所知晓的最广泛的含义，并且包括这样的片段(moiety)：其占据了正常由与母化合物或化学结构特征相连的一个或多个氢原子占据的位置。
在本申请中，术语“C1-C15的烷基”是指碳数1～15的直链或支链的烷基，烷基的示例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、1-甲基丁基、2-甲基丁基、异戊基、1-乙基丙基、1，1-二甲基丙基、1,2-二甲基丙基、新戊基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、异己基、1-乙基丁基、2-乙基丁基、1，1-二甲基丁基、1，2-二甲基丁基、1，3-二甲基丁基、2，2-二甲基丁基、2，3-二甲基丁基、3，3-二甲基丁基、1，1，2-三甲基丙基、1，2，2-三甲基丙基或1-乙基-1-甲基丙基等基团。
在本申请中，术语“C6-C30的芳基”是指碳数6～30的闭合的芳族环或环体系。芳基的实例包括但不限于苯基、萘基、菲基、蒽基、联苯基(包括二连苯基、三联苯基)、三亚苯基、芘基、螺双芴基、
Figure PCTCN2022104663-appb-000006
基、苝基、茚基、薁基、以及苯并菲基。
在本申请中，术语“空间位阻基团”是指能够在空间排布造成的相互排斥作用的任何官能团。该空间位阻基团包括但不限于羟基、烷氧基、环烷氧基。
在本申请中，术语“C1-C15的烷氧基”是指直链或支链的C1-C15的烷基基团，或碳数1～15的环烷基基团，其中在每种情况中在两个碳原子之间存在一个或多个氧原子。烷氧基包括但不限于甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十三烷氧基、十四烷氧基、十五烷氧基、环氧乙烷基、环氧丙烷基、环氧己烷基、环氧辛烷基。
在上述实施例中，分散剂具有第一嵌段和第二嵌段的嵌段共聚物，其中，第一嵌段包括具有式Ⅰ)所示的第一重复结构单元和式Ⅱ)所示的第二重复结构单元，第二嵌段包括具有具有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元，上述这些结构能够使分散剂溶于溶剂中，并有助于浆料中其它组分的均匀分散，增加浆料中的固含量，从而提高浆料的稳定性。
在申请的一些实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、取代或未取代的C1-C12的烷基、取代或未取代的C6-C12的芳基。
在上述这些实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自上述基团，可使分散剂快速溶解于有机溶剂中，并吸附于浆料 中固体颗粒的表面，以有助于固体颗粒的均匀分散，进一步可以提高浆料中的固含量。而且浆料中各组分的均匀分散，还可以提高浆料的导电性，以降低具有该浆料的电极极片的电阻。
在本申请的一些具体实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、甲基、乙基、丙基、丁基、戊基、正己、苯基和苄基中的至少一种。
在上述这些实施例中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、甲基、乙基、丙基、丁基、戊基、正己、苯基和苄基中的至少一种，有助于进一步提高浆料中的固含量，以及降低具有该浆料的电极极片的电阻。
在本申请的一些实施例中，当R 1、R 2、R 3、R 4和R 5分别选自氢时，第一重复结构单元具有式Ⅴ)的结构式：
Figure PCTCN2022104663-appb-000007
当R 6和R 7分别选自氢时，第二重复结构单元为乙烯。
在上述这些实施例中，第一重复结构单元具有上述结构式，以及第二重复结构单元为乙烯，可有助于分散剂牢固的吸附于浆料中固体颗粒的表面，使固体颗粒均匀分散。
在本申请的一些实施例中，第一嵌段为第一重复结构单元和第二重复结构单元的无规共聚嵌段。
在上述这些实施例中，第一嵌段为第一重复结构单元和第二重复结构单元的无规共聚嵌段，这样可降低分散剂的制备难度。
在本申请的一些实施例中，第一嵌段的重均分子量在1000-500000范围内。
在上述这些实施例中，第一嵌段的重均分子量在上述范围内，可有助于浆料中固体颗粒的均匀分散，提高浆料中的固含量。
示例性的，第一嵌段的重均分子量可以为1000、2000、3000、4000、5000、6000、7000、8000、9000或更高。
在本申请的实施例中，第二嵌段包括具有具有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元，其中，式III)所示的第三重复结构单元可以作为空间位阻基团，与式Ⅳ)所示的第四重复结构单元进行无规共聚以形成无规共聚嵌段，这样能够分散剂分子之间具有较大的空间位阻，减少浆料中组分团聚的发生。
在本申请的一些实施例中，R 8选自羟基、羧基、吡咯烷酮、环氧乙烷、环氧丙烷、卤素、取代或未取代的C1-C15的烷基、取代或未取代的C1-C15的烷氧基。
在上述这些实施例中，R 8选自上述基团，使分散剂分子之间具有更大的空间位阻，减少浆料中组分团聚的发生。
在本申请的一些实施例中，R 9、R 10分别独立地选自羟基、羧基、吡咯烷酮、环氧乙烷、环氧丙烷、卤素、取代或未取代的C1-C15的烷基、取代或未取代的C1-C15的烷氧基，其中，R 9和R 10可连接在一起为R 9-O-R 10或R 9-NH-R 10。
在上述这些实施例中，R 9和R 10选自上述基团，能够使分散剂分子之间具有较大的空间位阻的同时，还能够使分散剂有助于提高浆料中各组分的分散效果。
在本申请的一些实施例中，第二嵌段的重均分子量在1000-500000范围内。
在上述这些实施例中，第二嵌段的重均分子量在上述范围内，可使分散剂减少浆料中组分团聚的发生，还可有助于浆料中各组分的均匀分散。
示例性的，第二嵌段的重均分子量可以为1000、2000、3000、4000、5000、6000、7000、8000、9000或更高。
在本申请的一些实施例中，第一嵌段和第二嵌段物的平均聚合度比为(0.1-10)：1。
在上述这些实施例中，第一嵌段和第二嵌段的平均聚合度在上述范围内，可提高浆料中各组分的分散效果，并进一步提高浆料中的固含量，使浆料具有较好的稳定性。
分散剂的制备
本申请实施例提供了一种如上述任一项实施例中分散剂的制备方法，包括：
S10：将引发剂、链转移剂溶解于有机溶剂中，并于惰性氛围下搅拌，得到混合溶液；
S20：向混合溶液内添加第一嵌段的单体进行第一共聚反应；
S30：待第一共聚反应完成后，再添加第二嵌段的单体进行第二共聚反应；
S40：待第二共聚反应完成后，所产生的产物经沉淀、过滤、干燥，得到分散剂。
在上述实施例中，制备工艺简单，且制备安全。所制备得到的分散剂溶于溶剂中，有助于浆料中其它组分的均匀分散，增加浆料中的固含量，从而提高浆料的稳定性。
在本申请的一些实施例中，S10步骤中搅拌的速率在20min/rpm-1500min/rpm范围内。
在上述这些实施例中，搅拌线速度在上述范围内，可有助于引发剂和链转移剂溶解于溶剂中，利于第一共聚反应和第二共聚反应的发生。
在本申请的一些实施例中，S20步骤中的第一共聚反应的反应温度在-20℃-120℃。
在上述这些实施例中，第一共聚反应的反应温度在上述范围内，可提高第一共聚反应中产物的产率。
在本申请的一些实施例中，引发剂可以为任意一种或多种用于共聚反应的引发剂，例如偶氮类化合物。示例性的，引发剂可以但不局限于为偶氮二异丁腈(简称为AIBN)。
在本申请的一些实施例中，链转移剂可以为任意一种或多种用于共聚反应的链转移剂，本申请实施例对此不做具体限制。示例性的，链转移剂可以具有式Ⅵ)的结构式：
Figure PCTCN2022104663-appb-000008
其中，R 11选自C1-C5的烷基。
用于形成电极膜层的浆料组合物
本申请实施例提供了一种用于形成电极膜层的浆料组合物，包括上述任一项实施例中的分散剂以及粘结剂、活性材料和任选的导电剂。
在上述实施例中，浆料组合物由于包括上述实施例中的分散剂，因此，该浆料组合物具有较高的固含量，进而形成的浆料具有良好的稳定性，从而有助于提高电池的性能。
在本申请的一些实施例中，粘结剂可以包括但不限于聚丙烯酸钠、聚丙烯酰胺、聚丙烯酸、聚丙烯酸酯、聚丙烯腈、丁苯橡胶、聚四氟乙烯、聚偏氟乙烯、聚乙烯醇中的至少一种。
在本申请的一些实施例中，导电剂可以包括但不限于超导碳、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。
在本申请的一些实施例中，浆料组合物按总质量分数为100％计包含:
分散剂，0.01％-10％；
粘结剂，0.5％-10％；
活性材料，82％-91.99％；
导电剂，0％-15％。
在上述这些实施例中，合理选择各组分的含量，能够进一步提高浆料的稳定性。
在本申请的一些实施例中，活性材料为正极活性材料，该正极活性材料可以采用任何一种或多种用于电池的正极活性材料。
示例性的，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(简称为NCM333)、LiNi 0.5Co 0.2Mn 0.3O 2(简称为NCM523)、LiNi 0.5Co 0.25Mn 0.25O 2(简称为NCM211)、LiNi 0.6Co 0.2Mn 0.2O 2(简称为NCM622)、LiNi 0.8Co 0.1Mn 0.1O 2(简称为NCM811)、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(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。
在本申请的另一些实施例中，活性材料还可以为负极活性材料，该负极活性材料可以采用任何一种或多种用于电池的负极活性材料。
示例性的，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。
在上述实施例中，分散剂能够更换吸附于正极活性材料表面，使其均匀分散，从而可以进一步提高电池的性能。
浆料组合物的制备
本申请实施例提供了一种浆料组合物的制备方法，包括：
S50：将导电剂、分散剂和部分溶剂在搅拌条件下混合，得到第一混合物；
S60：将粘结剂添加至第一混合物进行搅拌混合，得到第二混合物；
S70：将活性材料和余量溶剂添加至第二混合物进行搅拌混合，得到浆料组合物。
在上述这些实施例中，通过优化组分的加料顺序，提高制浆效率。
在本申请的实施例中，由于采用了上述实施例中的分散剂，可降低浆料的搅拌线速度及搅拌时间。在本申请的一些实施例中，S50步骤中的搅拌线速度为2m/s-10m/s，搅拌时间为5min-40min；S60步骤中的搅拌线速度2m/s-10m/s，搅拌时间为5min-40min；S70步骤中的搅拌线速度为2m/s-10m/s，搅拌时间为150min-220min。
电极极片
本申请实施例提供了一种电极极片，包括集流体和活性材料层，其中，活性材料层设于集流体的至少一个表面，活性材料层使用上述任一项实施例中的浆料组合物形成。
在上述实施例中，由于电极极片的活性材料层使用上述实施例的浆料组合物，因此，该电极极片具有较低的电阻，并且能够提高电池的循环性能。
在本申请的一些实施例中，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。
二次电池
本申请实施例提供了一种二次电池，包括正极极片、负极极片和隔膜。隔膜设于正极极片和负极极片之间。其中，正极极片和/或负极极片为上述实施例中的电极极片。
在上述实施例中，由于正极极片和/或负极极片为上述实施例中的电极极片，因此，该电池具有较好的循环性能。
在本申请的一些实施例中，正极极片为上述实施例中的电极极片，则活性材料层为正极活性材料层。该正极极片可以通过以下方法制备得到：将上述的正极浆料组合物涂覆在正极集流体的至少一个表面上，干燥，冷压，得到正极极片。
在本申请的一些实施例中，负极极片为上述实施例中的电极极片，则活性材料层为负极活性材料层。该负极极片可以通过以下方法制备得到：将上述的负极浆料组合物涂覆在负极集流体的至少一个表面上，干燥，冷压，得到负极极片。
本申请对隔膜的种类没有特别的限制，可以采用任何一种或多种具有良好的化学稳定性和机械稳定性的多孔结构隔膜。
在本申请的一些实施例中，隔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。
在本申请的实施例中，还包括电解质，该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。
在本申请的一些实施例中，电解质为液态的，且包括电解质盐和溶剂。
在本申请的一些实施例中，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。
在本申请的一些实施例中，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、碳酸乙烯酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在本申请的一些实施例中，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。
将上述正极极片、隔膜、负极极片按顺序堆叠好，使隔膜处于正极极片、负极极片之间起到隔离的作用，得到电极组件，也可以是经卷绕后得到电极组件；在电极组件上连接极耳，并将电极组件置于包装外壳中，再经过加热去除多余的水，然后注入电解质并封口；最后经过静置、热冷压、化成、整形、容量测试等工序，得到本申请的二次电池。
电池模块
本申请实施例提供了一种电池模块，包括上述实施例中的二次电池。由于包括了上述实施例中的二次电池，因此，该电池模块也具有上述二次电池所具有的技术效果，在此不做赘述。
电池包
本申请实施例提供了一种电池包，包括上述实施例中的二次电池或上述实施例中所述的电池模块。由于包括了上述实施例中的二次电池或电池模块，因此，该电池包也具有上述二次电池或电池模块所具有的技术效果，在此不做赘述。
用电装置
本申请实施例提供了一种用电装置，包括上述实施例中的二次电池、上述实施例中的电池模块或上述实施例中的电池包。由于包括了上述实施例中的二次电池、电池模块或电池包，因此，该用电装置具有较长的使用寿命及续航里程。
以下通过具体实施例对分散剂及其制备方法、浆料组合物和二次电池进行详细说明。
实施例1
分散剂的制备
分散剂的具体制备步骤如下：
(1)将0.025mol AIBN和0.05mol RAFT试剂溶解在300mL二氧六环中，在氮气氛围下，搅拌1h，得到混合溶液；
(2)将0.25mol苯乙烯与0.25mol乙烯加入混合溶液中进行第一共聚反应，反应温度为60℃，反应时间为6h；
(3)待第一共聚反应完成后，将0.25mol马来酸酐与0.25mol具有式Ⅲ)的化合物(R 8为环氧乙烷)，n＝12进行第二共聚反应，反应6h；
(4)待第二共聚反应完成后，所产生的产物经沉淀、过滤、干燥，得到如下结构式的分散剂。
正极极片的制备
正极极片的具体制备步骤如下：
(1)将碳纳米管、分散剂和部分N-甲基吡咯烷酮溶剂(大约为溶剂的总重量的90％)在搅拌条件下进行混合，得到第一混合物，其中，搅拌线速度为3m/s，搅拌时间为5min；
(2)将PVDF和第一混合物进行搅拌混合，得到第二混合物，其中，搅拌线速度为4m/s，搅拌时间为5min；
(3)将磷酸铁锂和余量N-甲基吡咯烷酮溶剂添加至第二混合物中进行搅拌混合，得到正极浆料，其中，搅拌线速度为5m/s，搅拌时间为170min；
(4)将正极浆料涂覆于铝箔表面上，经烘干、冷压后，得到正极极片；
其中，上述磷酸铁锂、碳纳米管、PVDF和分散剂的重量比为91.9：5：3：0.1。
负极极片的制备
负极极片的具体制备步骤如下：
(1)将人造石墨/氧化亚硅、Super P、聚偏四氟乙烯(简称为PVDF)按照重量比为96：2：2在去离子水溶剂体系中充分搅拌混合均匀后，得到负极浆料；
(2)将负极浆料涂覆于铜箔上，经烘干、冷压后，得到负极极片。
电解质的制备
在氩气气氛手套箱中(H 2O<0.1ppm，O 2<0.1ppm)，将碳酸乙烯酯(简称为EC)和碳酸甲乙酯(简称为EMC)按照体积比3:7混合均匀得到有机溶剂，再加入12.5％六氟磷酸锂(简称为LiPF 6)溶解于上述有机溶剂中，搅拌均匀，得到电解质。
隔膜
以聚乙烯膜作为隔膜。
二次电池的制备
将上述正极极片、隔膜、负极极片按顺序叠好，使隔膜处于正、负极极片之间起到隔离的作用；然后卷绕得到电极组件，给电极组件焊接极耳，并将电极组件装入铝壳中，并在80℃下烘烤去除水分，随即注入上述电解质并封口；最后经过静置、热冷压、化成、整形等工序，得到本实施例的二次电池。
实施例2-26以及对比例1
实施例2-26与对比例1的二次电池，其制备方法与实施例1相似，不同之处分别列于表1，其中，在实施例17中，第一重复结构单元具有式(A)的结构式，第二重复结构单元具有式(B)的结构式，第四重复结构单元具有式(C)的结构式。
Figure PCTCN2022104663-appb-000009
在实施例18中，第一重复第一重复结构单元具有式(D)的结构式，第二重复结构单元具有式(E)的结构式，第四重复结构单元具有式(F)的结构式。
Figure PCTCN2022104663-appb-000010
在实施例19中，第一重复第一重复结构单元具有式(H)的结构式，第二重复结构单元具有式(M)的结构式，第四重复结构单元具有式(G)的结构式。
Figure PCTCN2022104663-appb-000011
正极浆料中固含量的测试
将正极浆料涂覆于铝箔上，经烘干，得到正极极片。其中，正极浆料固含量W的计算公式如下：
W＝(m 1-m 0)/(m 2-m 0)×100％
其中，m 0为铝箔的质量，m 1为烘干后的正极极片的质量，m 2为正极浆料涂覆铝箔后所得到湿正极极片的质量。
正极极片的电阻率测试
使用晶格电子ST2263型双电测数字式四探针测试仪直接测试膜片电阻率。
电池容量保持率的测试
在25℃的环境中，将二次电池以1C恒流充电至3.65V，然后在0.5C的放电电流下进行恒流放电至2.5V，测得的放电容量记为初始容量C 0。对同一个电池重复以上步骤，并同时记录循环n次后电池的放电容量C n，循环n次后电池容量保持率P n＝100％×C n/C 0。其中，第一次对应n＝1、第二次循环对应n＝2……第100次循环对应n＝100。测定循环1000次后的电池容量保持率，测试结果如表1所示。
表1
Figure PCTCN2022104663-appb-000012
Figure PCTCN2022104663-appb-000013
注：T 总表示正极浆料组合物形成的搅拌总时间，单位为min；
W表示浆料中的固含量，单位为％；
Z表示正极极片的电阻率，单位为Ω.cm；
K表示电池在25℃下循环1000次后的容量保持率，单位为％。
由表1可知，本申请实施例提供的分散剂能够提高浆料中的固含量，使浆料具有较好的稳定性。并且该浆料能够使电极极片具有较低的电阻，以及还使电池具有较好的的容量保持率和循环性能。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有实施例。

Claims (18)

  1. 一种分散剂，包括具有第一嵌段和第二嵌段的嵌段共聚物；
    所述第一嵌段包括具有式Ⅰ)所示的第一重复结构单元和式Ⅱ)所示的第二重复结构单元：
    Figure PCTCN2022104663-appb-100001
    其中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、羰基、羧基、硝基、磺酸基、酰胺、酯基、取代或未取代的C1-C15的烷基、取代或未取代的C1-C15的烷氧基、取代或未取代的C6-C30的芳基；
    所述第二嵌段包括具有式III)所示的第三重复结构单元和式Ⅳ)所示的第四重复结构单元：
    Figure PCTCN2022104663-appb-100002
    其中，平均聚合度n为1-25中的任意一个整数，R 8、R 9、R 10的偶极矩大于2×10 -30C·m；
    可选地，R 8、R 9、R 10分别独立地选自羟基、羧基、吡咯烷酮、环氧乙烷、环氧丙烷、卤素、取代或未取代的C1-C15的烷基、取代或未取代 的C1-C15的烷氧基，其中，R 9和R 10可连接在一起为R 9-O-R 10、R 9-NH-R 10。
  2. 根据权利要求1所述的分散剂，其中，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、取代或未取代的C1-C12的烷基、取代或未取代的C6-C12的芳基；
    可选地，R 1、R 2、R 3、R 4、R 5、R 6和R 7分别独立地选自氢、卤素、氰基、甲基、乙基、丙基、丁基、戊基、正己、苯基和苄基中的至少一种。
  3. 根据权利要求1或2所述的分散剂，其中，所述第一重复结构单元具有如下结构式：
    Figure PCTCN2022104663-appb-100003
    所述第二重复结构单元为乙烯。
  4. 根据权利要求1至3任一项所述的分散剂，其中，所述第一嵌段为所述第一重复结构单元和所述第二重复结构单元的无规共聚嵌段。
  5. 根据权利要求1至4中任一项所述的分散剂，其中，所述第一嵌段的重均分子量在1000-500000范围内。
  6. 根据权利要求1-5中任一项所述的分散剂，其中，所述第二嵌段的重均分子量在1000-500000范围内。
  7. 根据权利要求1-6中任一项所述的分散剂，其中，所述第一嵌段和第二嵌段物的平均聚合度比为(0.1-10)：1。
  8. 一种如权利要求1-7中任一项所述分散剂的制备方法，包括：
    将引发剂、链转移剂溶解于有机溶剂中，并于惰性氛围下搅拌，得到混合溶液；
    向所述混合溶液内添加第一嵌段的单体进行第一共聚反应；
    待第一共聚反应完成后，再添加第二嵌段的单体进行第二共聚反应；
    待第二共聚反应完成后，所产生的产物经沉淀、过滤、干燥，得到所述分散剂。
  9. 根据权利要求8所述的制备方法，其中，所述搅拌的速率在20min/rpm-1500min/rpm范围内；
    可选的，所述第一共聚反应的反应温度在-20℃-120℃。
  10. 一种用于形成电极膜层的浆料组合物，包括权利要求1-7中任一项所述的分散剂以及粘结剂、活性材料和任选的导电剂。
  11. 根据权利要求10所述的浆料组合物，其中，所述浆料组合物按总质量分数为100％计包含:
    分散剂，0.01％-10％；
    粘结剂，0.5％-10％；
    活性材料，82％-91.99％；
    导电剂，0％-15％。
  12. 根据权利要求10或11所述的浆料组合物，其中，所述活性材料为正极活性材料。
  13. 一种如权利要求10-12中任一项所述的浆料组合物的制备方法，包括：
    将导电剂、分散剂和部分溶剂在搅拌条件下混合，得到第一混合物；
    将粘结剂添加至所述第一混合物进行搅拌混合，得到第二混合物；
    将活性材料和余量溶剂添加至所述第二混合物进行搅拌混合，得到所述浆料组合物。
  14. 一种电极极片，包括：
    集流体；
    活性材料层，设于所述集流体的至少一个表面，所述活性材料层使用权利要求10-12中任一项中所述的浆料组合物形成。
  15. 一种二次电池，其中，包括：
    正极极片；
    负极极片；
    隔膜，设于所述正极极片和所述负极极片之间；
    其中，所述正极极片和/或所述负极极片为权利要求14所述的电极极片。
  16. 一种电池模块，包括权利要求15中所述的二次电池。
  17. 一种电池包，包括权利要求15中所述的二次电池或权利要求16中所述的电池模块。
  18. 一种用电装置，包括权利要求15中所述的二次电池、权利要求16中所述的电池模块或权利要求17中所述的电池包。
PCT/CN2022/104663 2022-07-08 2022-07-08 分散剂及其制备方法、浆料组合物及其制备方法、电极极片和包括该电极极片的装置 WO2024007310A1 (zh)

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