WO2022067709A1 - 复合粘结剂和包含其的电化学装置及电子装置 - Google Patents

复合粘结剂和包含其的电化学装置及电子装置 Download PDF

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Publication number
WO2022067709A1
WO2022067709A1 PCT/CN2020/119509 CN2020119509W WO2022067709A1 WO 2022067709 A1 WO2022067709 A1 WO 2022067709A1 CN 2020119509 W CN2020119509 W CN 2020119509W WO 2022067709 A1 WO2022067709 A1 WO 2022067709A1
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negative electrode
binder
active material
electrode active
composite binder
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English (en)
French (fr)
Inventor
李嘉文
石长川
张青文
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to CN202080009974.XA priority Critical patent/CN113330610B/zh
Priority to PCT/CN2020/119509 priority patent/WO2022067709A1/zh
Publication of WO2022067709A1 publication Critical patent/WO2022067709A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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 technical field of energy storage, and in particular, to a composite binder and electrochemical devices and electronic devices comprising the composite binder.
  • electrochemical devices eg, lithium-ion batteries
  • power electronic devices need to exhibit higher energy density, higher rate, higher safety, and less capacity fading after repeated charge-discharge processes.
  • the present application provides a composite binder and electrochemical devices and electronic devices including the composite binder in an attempt to at least to some extent solve at least one problem existing in the related art.
  • the present application provides a composite binder, the composite binder comprising: a polymer binder and a fiber reinforcement, wherein the polymer binder is a solution-type binder, which comprises Homopolymer or copolymer, the monomer of the homopolymer or the copolymer includes at least one of acrylic acid, alginic acid, acrylonitrile, acrylamide, vinyl alcohol.
  • the polymer binder is a solution-type binder, which comprises Homopolymer or copolymer, the monomer of the homopolymer or the copolymer includes at least one of acrylic acid, alginic acid, acrylonitrile, acrylamide, vinyl alcohol.
  • the structural strength of the negative electrode active material layer can be effectively improved, so that the electrochemical device has good cycle performance and safety performance.
  • the present application provides an electrochemical device including a positive electrode, a separator, and a negative electrode.
  • the negative electrode comprises a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer comprises a silicon-based material, a carbon-based material and the composite binder in the above embodiment.
  • the present application provides an electronic device comprising the above electrochemical device.
  • FIG. 1 is a schematic diagram of a composite adhesive according to some embodiments of the present application.
  • Figure 2 is a graph showing the tensile strength of the composite binder formed by mixing the polymer binder and the fiber reinforcement at different weight ratios.
  • Figure 3 is a graph showing the tensile strength of a composite binder formed by mixing various polymer binders with different fiber reinforcements in the same proportion.
  • the terms “substantially,” “substantially,” “substantially,” and “about” are used to describe and account for small variations. When used in conjunction with an event or circumstance, the term can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs in close approximation.
  • the term when used in conjunction with a numerical value, the term may refer to a range of variation of less than or equal to ⁇ 10% of the numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to Equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • the difference between two values is less than or equal to ⁇ 10% of the mean of the value (e.g., less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 3%, equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%), then the two values may be considered "substantially" the same.
  • a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
  • the phrase “at least one of A and B” means A only; B only; or A and B.
  • the phrase "at least one of A, B, and C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single element or multiple elements.
  • Item B may contain a single element or multiple elements.
  • Item C may contain a single element or multiple elements.
  • alginic acid refers to a linear block polyuronic acid consisting of a homopolymeric The blocks and the cross-polymerized blocks of these two uronic acids are connected by 1,4-glycosidic bonds to form an organic acid polymer.
  • alginates refers to derivatives formed by alginic acid and salts, including, but not limited to, at least one of calcium salts, magnesium salts, sodium salts, potassium salts, and strontium salts.
  • polyethylene-based polymer refers to a polymer composed of vinyl monomers, which can be derivatives of vinyl and functional groups of any substituent, including, but not limited to, vinyl alcohol.
  • polyvinyl alcohol is expected to be a polymer composed of vinyl alcohol monomers.
  • polypropylene polymer refers to a polymer composed of propylene monomers, which can be derivatives of propylene and any substituted functional group, including, but not limited to, acrylic acid, propylene At least one of nitrile and acrylamide.
  • polyacrylic acid is expected to be a polymer composed of acrylic monomers.
  • Polyacrylonitrile is expected to be a polymer composed of acrylonitrile monomers.
  • Polyacrylamide is expected to be a polymer composed of acrylamide monomers.
  • carboxymethyl cellulose refers to cellulose having carboxymethyl, carboxyethyl, and carboxypropyl substituents, respectively.
  • carboxymethyl cellulose salts refer to carboxymethyl cellulose, carboxyethyl cellulose and carboxypropyl cellulose, respectively.
  • the derivatives formed with salts include, but are not limited to, at least one of calcium salts, magnesium salts, sodium salts, potassium salts, and strontium salts.
  • fibers refers to solid fibers with relatively low solubility.
  • silicon-based materials are the mainstream anode active materials for the development of electrochemical devices with high volumetric energy density (eg, lithium-ion batteries) in the future due to their theoretical gram capacity as high as 4200 mAh/g.
  • Such high-energy-density anode active materials have a huge volume change effect (for example, greater than about 300%) in the process of lithium deintercalation, and the severe expansion of the anode will cause the interface between the anode and the separator to deform or even separate, thereby causing lithium-ion batteries. decreased cycle performance. Therefore, excessive volume expansion during the charge-discharge cycle will not only cause the electrode assembly to deform and reduce the cycle performance, but also easily lead to the destruction of the structure of the lithium-ion battery, which seriously affects the safety of the lithium-ion battery.
  • the present application studies to improve the bonding ability (cohesion) between the particles of the negative electrode active material in the negative electrode active material layer to suppress the cyclic expansion of the negative electrode during charging.
  • the present application provides a composite binder with high bonding and high toughness properties. By adding it to the negative electrode active material to bond and coat the particle surface of the negative electrode active material, a bridge between particles is formed, so as to effectively Improve the cohesion of the negative electrode.
  • the composite binder of the present application comprises a polymer binder and a fiber reinforcement, so that the composite binder has higher strength, toughness and heat resistance.
  • the fiber reinforcement has a high degree of orientation and crystallinity (eg, between 50% and 70%), the tensile strength of the composite binder can be effectively improved.
  • the hydroxyl groups of the fiber reinforcement and the carboxyl groups and hydroxyl groups of the polymer binder can chemically bond or generate hydrogen bonds to form a good composite structure.
  • This composite structure can take advantage of the high tensile strength of the fiber reinforcement. It can support the negative electrode active material during the charging process, reduce the deformation degree and expansion rate of the negative electrode during the charging and discharging cycle, and ensure the cycle performance and rate performance of the electrochemical device.
  • an embodiment of the present application provides a composite adhesive, which includes: a polymer adhesive and a fiber reinforcement.
  • the polymer binder is a solution-type binder, which includes a homopolymer or a copolymer, and the monomers of the homopolymer or the copolymer include acrylic acid, alginic acid, acrylonitrile, acrylamide, and vinyl alcohol. at least one.
  • the fiber reinforcement comprises cellulose fibers, carboxymethyl cellulose fibers and derivatives thereof, hydroxyethyl cellulose fibers and derivatives thereof, hydroxypropyl cellulose fibers and derivatives thereof, and polyvinyl alcohol at least one of the fibers. In some embodiments, the fiber reinforcement consists of polyvinyl alcohol fibers.
  • the polymeric binder has a weight average molecular weight of 100 kDa to 10,000 kDa. In other embodiments, the polymeric binder has a weight average molecular weight of approximately, eg, about 100 kDa, about 200 kDa, about 500 kDa, about 1000 kDa, about 2000 kDa, about 5000 kDa, about 8000 kDa, about 10000 kDa, or any two of these values range composed of.
  • the fiber reinforcements are elongated fibers.
  • the length of the fiber reinforcement is 5 ⁇ m to 100 ⁇ m. In other embodiments, the length of the fiber reinforcement is approximately, for example, about 5 ⁇ m, about 10 ⁇ m, about 20 ⁇ m, about 30 ⁇ m, about 40 ⁇ m, about 50 ⁇ m, about 75 ⁇ m, about 100 ⁇ m, or a range of any two of these values .
  • the diameter of the fiber reinforcement is 0.001 ⁇ m to 1.0 ⁇ m. In other embodiments, the diameter of the fiber reinforcement is approximately, eg, about 0.001 ⁇ m, about 0.01 ⁇ m, about 0.05 ⁇ m, about 0.1 ⁇ m, about 0.2 ⁇ m, about 0.3 ⁇ m, about 0.4 ⁇ m, about 0.5 ⁇ m, about 1.0 ⁇ m or a range of any two of these values.
  • length and diameter are commonly used parameters to simplify the description of the morphology of the fiber reinforcement; the length is the fiber length from one end to the other end of the fiber reinforcement measured by scanning electron microscopy. The diameter is the fiber diameter of the cross-section of the fiber reinforcement.
  • the length to diameter ratio of the fiber reinforcement is 100 to 10,000. In other embodiments, the fiber reinforcement has an aspect ratio approximately, eg, about 100, about 200, about 500, about 1000, about 2500, about 5000, about 10000, or a range of any two of these values.
  • FIG. 1 is a schematic diagram of a composite adhesive according to some embodiments of the present application.
  • the fiber reinforcements 20 are still in the form of elongated solid fibers in the polymer binder 10 .
  • the composite binder has a solids content of 1% to 60%. In other embodiments, the solids content of the composite binder is approximately, for example, about 1%, about 2%, about 5%, about 10%, about 20%, about 50%, about 60%, or any of these values A range of any two.
  • solid content refers to the weight percent of all solids in the solution, for example, the solid content of the composite binder includes the solid content of both the "polymer binder" and the "fiber reinforcement".
  • the method for testing the solid content of the composite binder provided in some examples of this application is to dry the composite binder at 130°C to 200°C, and calculate the weight ratio of the remaining solids after drying.
  • the particle size Dv50 of the composite binder is 1 ⁇ m to 100 ⁇ m. In other embodiments, the particle size Dv50 of the composite binder is approximately, eg, about 1 ⁇ m, about 5 ⁇ m, about 10 ⁇ m, about 20 ⁇ m, about 50 ⁇ m, about 100 ⁇ m, or a range of any two of these values.
  • particle size represents the characteristic particle characteristic Dv50 of a sample obtained by laser particle size testing, where Dv50 represents the particle size of the material in the volume-based particle distribution, starting from the small particle size side and reaching 50% of the volume cumulative.
  • the particle size test method provided in the examples of this application is to use a Mastersizer 2000 laser particle size distribution tester to analyze the particle size of the particles of the sample: disperse the sample in 100 mL of dispersant (deionized water), so that the shading degree reaches 8-12% . The samples were then sonicated for 5 minutes at an ultrasonic intensity of 40KHz and 180w. After sonication, the sample is subjected to laser particle size distribution analysis to obtain particle size distribution data.
  • the composite binder can effectively improve the tensile strength by mixing a certain proportion of polymer binder (for example, polyacrylic acid, PAA) and fiber reinforcement (for example, polyvinyl alcohol fiber). , thereby providing good cohesion among the particles of the negative active material.
  • polymer binder for example, polyacrylic acid, PAA
  • fiber reinforcement for example, polyvinyl alcohol fiber
  • the tensile strength of the composite binder formed by using polyacrylic acid as the polymer binder and using polyvinyl alcohol fiber as the fiber reinforcement can reach 3100 MPa.
  • the composite binder has a tensile strength of 1000 MPa to 3100 MPa.
  • tensile strength represents the critical value of the transition of the sample from uniform plastic deformation to localized concentrated plastic deformation, and tensile strength is the resistance that characterizes the maximum uniform plastic deformation of the material.
  • the tensile strength test method provided in some embodiments of the present application includes: loading a binder sample into a mold with a fixed area (width 10mm and length 100mm), drying it to prepare an adhesive film with a thickness of 2mm to 3mm, taking A uniform section in the middle in the length direction to obtain a sample strip with an area of 10mm x 30mm.
  • the stress-strain curve of the sample strip was tested by a high-speed rail tensile machine (AL-3000), the tensile speed was 50 mm/min, 3 sets of parallel samples were tested each time, and it was recorded that the stress-strain curve of the sample strip could not show a uniform line-line curve
  • the average value of the maximum stress at the time is the tensile strength.
  • the weight ratio of polymeric binder to fiber reinforcement is 1:10 to 50:1. In other embodiments, the weight ratio of polymeric binder to fiber reinforcement is approximately, eg, about 1:10, about 1:5, about 1:1, about 10:1, about 50:1, or these A range of any two of the values. In other embodiments, the weight ratio of polymer binder to fiber reinforcement is 1:6 to 40:1.
  • the preparation method of the composite binder provided by the present application is to uniformly mix a fixed weight ratio of the polymer binder with the fiber reinforcement. It should be understood that the preparation method of the composite binder in the embodiments of the present application, without departing from the spirit of the present application, may select other preparation methods capable of realizing the functions of the present application according to specific needs, and is not limited thereto.
  • an embodiment of the present application provides an electrochemical device, the electrochemical device includes a positive electrode, a separator, and a negative electrode.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer includes the composite binder in the above embodiment.
  • the electrochemical device is a lithium-ion battery.
  • the negative electrode current collector may be copper foil or nickel foil, however, other negative electrode current collectors capable of realizing the functions of the present application may be used without limitation.
  • the negative electrode active material layer contains a negative electrode active material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as "a negative electrode active material capable of absorbing/releasing lithium Li”).
  • a negative electrode active material capable of absorbing/releasing lithium (Li) may include carbon-based materials, metal compounds, oxides, sulfides, lithium nitrides such as LiN3, lithium metal, metals alloyed with lithium, and polymer materials.
  • examples of materials with particularly high energy density include silicon, tin, germanium, antimony, bismuth, aluminum, alloys, or compounds thereof.
  • the theoretical specific capacity of silicon is as high as 4200mAh/g, which is more than ten times that of the traditional graphite anode (the theoretical specific capacity of graphite is 372mAh/g).
  • the anode active material layer further includes a silicon-based material and a carbon-based material.
  • the silicon-based material includes at least one of elemental silicon, silicon oxide, silicon alloy, and silicon carbon.
  • the carbon-based material includes at least one of natural graphite, artificial graphite, mesocarbon microspheres, soft carbon, and hard carbon.
  • the ratio of the weight of the carbon-based material to the weight of the silicon-based material is greater than 0 and less than or equal to 99.
  • the weight ratio of the composite binder is 1% to 20% based on the total weight of the negative active material. In other embodiments, the weight ratio of the composite binder is approximately, for example, about 1%, about 2%, about 3%, about 4%, about 5%, about 10%, based on the total weight of the negative active material. %, about 11%, about 12%, about 13%, about 14%, about 15%, about 20%, or a range of any two of these values.
  • the negative electrode active material layer further includes a dispersant, which is a material soluble in an aqueous solution, wherein the dispersant includes carboxymethyl cellulose and its salts, hydroxyethyl cellulose and its salts, At least one of hydroxypropyl cellulose and its salts, polyethylene glycol and polyvinylpyrrolidone.
  • a dispersant which is a material soluble in an aqueous solution, wherein the dispersant includes carboxymethyl cellulose and its salts, hydroxyethyl cellulose and its salts, At least one of hydroxypropyl cellulose and its salts, polyethylene glycol and polyvinylpyrrolidone.
  • the weight of the dispersant is less than about 2% based on the total weight of the negative active material layer. In other embodiments, the weight of the dispersant is less than about 1% based on the total weight of the negative active material.
  • the negative active material layer further includes a conductive agent, wherein the conductive agent includes at least one of conductive carbon black, ketjen black, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanofibers .
  • the conductive agent includes at least one of conductive carbon black, ketjen black, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanofibers .
  • the weight of the conductive agent is less than about 2% based on the total weight of the negative active material layer. In other embodiments, the weight of the conductive agent is less than about 1% based on the total weight of the negative active material.
  • the positive electrode includes a positive current collector.
  • the positive electrode current collector may be aluminum foil or nickel foil, however, other positive electrode current collectors capable of realizing the functions of the present application may be used without limitation.
  • the positive electrode includes a positive electrode active material layer.
  • the positive electrode active material layer includes a positive electrode active material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as a "positive electrode active material capable of absorbing/releasing lithium Li").
  • the cathode active material capable of absorbing/releasing lithium (Li) may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, One or more of lithium iron phosphate, lithium titanate, and lithium-rich manganese-based materials.
  • the chemical formula of lithium cobaltate may be Li y Co a M1 b O 2-c , wherein M1 represents selected from nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al) , Boron (B), Titanium (Ti), Vanadium (V), Chromium (Cr), Iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin (Sn), Calcium (Ca) , at least one of strontium (Sr), tungsten (W), yttrium (Y), lanthanum (La), zirconium (Zr), and silicon (Si), the values of y, a, b and c are respectively within the following ranges: 0.8 ⁇ y ⁇ 1.2, 0.8 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.2, -0.1 ⁇ c ⁇ 0.2;
  • the chemical formula of nickel cobalt lithium manganate or nickel cobalt aluminate can be Li z Ni d M2 e O 2-f , wherein M2 is selected from cobalt (Co), manganese (Mn), magnesium (Mg), Aluminum (Al), Boron (B), Titanium (Ti), Vanadium (V), Chromium (Cr), Iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin At least one of (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr) and silicon (Si), the values of z, d, e and f are respectively within the following ranges: 0.8 ⁇ z ⁇ 1.2, 0.3 ⁇ d ⁇ 0.98, 0.02 ⁇ e ⁇ 0.7, -0.1 ⁇ f ⁇ 0.2;
  • the chemical formula of lithium manganate is Li u Mn 2-g M 3g O 4-h , wherein M3 is selected from cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al) , Boron (B), Titanium (Ti), Vanadium (V), Chromium (Cr), Iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin (Sn), Calcium (Ca) , at least one of strontium (Sr) and tungsten (W), the values of z, g and h are respectively in the following ranges: 0.8 ⁇ u ⁇ 1.2, 0 ⁇ g ⁇ 1.0 and -0.2 ⁇ h ⁇ 0.2.
  • the positive electrode active material layer can further include at least one of a binder and a conductive agent. It should be understood that those skilled in the art can select other binders and conductive agents that can realize the functions of the present application according to actual needs, but are not limited by them.
  • the release film includes, but is not limited to, at least one selected from polyethylene, polypropylene, polyethylene terephthalate, polyimide, and aramid.
  • the polyethylene includes at least one component selected from the group consisting of high density polyethylene, low density polyethylene, and ultra-high molecular weight polyethylene.
  • the separator is polypropylene, and polypropylene has good affinity with the high molecular polymers in the above embodiments, which is beneficial to improve the adhesion between the adhesive layer and the separator.
  • the lithium ion battery of the present application further includes an electrolyte, and the electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolyte, and the electrolyte includes a lithium salt and a non-aqueous solvent.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , One or more of LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB and lithium difluoroborate.
  • LiPF 6 is chosen as the lithium salt because it gives high ionic conductivity and improves cycling characteristics.
  • the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
  • the above-mentioned carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
  • Examples of the above-mentioned other organic solvents are dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, Formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters and combinations thereof.
  • the non-aqueous solvent is selected from ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluorocarbon The group consisting of ethylene carbonate and combinations thereof.
  • the preparation methods of the positive electrode, the negative electrode, the separator and the electrolyte in the embodiments of the present application may select other preparation methods capable of realizing the functions of the present application according to specific needs, without being limited thereto .
  • the method for preparing a lithium ion battery includes: winding, folding or stacking the negative electrode, separator and positive electrode in the above-mentioned embodiments in sequence into an electrode assembly, and packing the electrode assembly into, for example, an electrode assembly.
  • the aluminum-plastic film is poured into the electrolyte, followed by vacuum packaging, standing, chemical formation, shaping and other processes to obtain a lithium-ion battery.
  • the adhesive layers of the present application can be used in other suitable electrochemical devices.
  • Such an electrochemical device includes any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • Some embodiments of the present application further provide an electronic device including the electrochemical device in the embodiments of the present application.
  • the electronic device in the embodiment of the present application is not particularly limited, and it may be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large-scale household storage batteries and lithium-ion capacitors, etc.
  • the lithium ion batteries formed in the following examples were disassembled to obtain a complete negative electrode, left standing for 5 minutes until the electrolyte was evaporated and dried, and a negative electrode with a size of 80mm ⁇ 30mm was cut out, and a high-speed iron tensile machine (AL-3000) was used to obtain the complete negative electrode. And set the tensile speed to 50mm/min and the tensile displacement to 50mm for cohesion test. From the following examples, four lithium-ion batteries were taken from each group, and the average value of the cohesion of the negative electrodes of the lithium-ion batteries was calculated.
  • the lithium-ion batteries formed in the following examples and comparative examples were placed in an incubator at 25°C ⁇ 2°C for 2 hours, charged with a constant current of 0.7C to 4.45V, and then charged with a constant voltage of 4.45V to 0.05C And let stand for 15 minutes; then discharge to 3.0V with 0.5C constant current, this is a charge-discharge cycle process, record the discharge capacity of the lithium-ion battery for the first cycle; The discharge capacity after 200 cycles was recorded.
  • the cycle capacity retention rate of the lithium ion battery discharge capacity at the 200th cycle (mAh)/discharge capacity after the first cycle (mAh) ⁇ 100%.
  • a 600g flat plate thickness gauge (ELASTOCON, EV 01) was used to test the thickness of the lithium-ion battery.
  • the lithium-ion batteries of the following examples and comparative examples were placed in an incubator at 25°C ⁇ 2°C for 2 hours, charged to 4.45V with a constant current of 0.7C, and then charged to 0.05C with a constant voltage of 4.45V and then charged to 0.05C. Let stand for 15 minutes, and record the thickness of the lithium-ion battery under full charge; then discharge to 3.0V at a constant current of 0.5C, this is a charge-discharge cycle process, and record the thickness of the lithium-ion battery in the first cycle of the lithium-ion battery; The method was repeated for 200 charge-discharge cycles, and the thickness of the lithium-ion battery was recorded after 200 cycles.
  • the cycle thickness expansion ratio of the lithium ion battery (the thickness of the lithium ion battery at the 200th cycle/the thickness of the lithium ion battery at the first cycle-1) ⁇ 100%.
  • Lithium cobaltate, conductive carbon black and polyvinylidene fluoride are dissolved in N-methylpyrrolidone (NMP) solution in a weight ratio of 97:1.4:1.6 to form a positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode is obtained after drying, cold pressing and cutting procedures.
  • the negative electrode slurry is coated on the negative electrode current collector, and the negative electrode is obtained after drying, cold pressing and cutting procedures.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • PP propyl propionate
  • VC ethylene carbonate Vinyl ester
  • a polyethylene film is used as the separator, and the positive electrode, separator and negative electrode are stacked in sequence, so that the separator is placed between the positive electrode and the negative electrode for isolation, and then wound into an electrode assembly.
  • the electrode assembly was put into an aluminum-plastic film packaging bag, and after dehydration at 80° C., a dry electrode assembly was obtained.
  • the above electrolyte was injected into the dry electrode assembly, and the preparation of the lithium ion batteries of the following examples and comparative examples was completed through the processes of vacuum packaging, standing, chemical formation, and shaping.
  • Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-9 are lithium ion batteries using carbon-based materials as negative electrodes, wherein the negative electrode formulations are shown in Table 1-1.
  • Table 1-1 the weight ratios of polymer binder and fiber reinforcement in the binders of Examples 1-1, 1-10 and Comparative Examples 1-8 and 1-9 are the same, other parameters of the binder are such as: The solid content, particle size, aspect ratio of fiber reinforcement and tensile strength are adjusted, please refer to Table 1-2 for details.
  • Table 1-2 shows the solid content, particle size and tensile strength of the composite binders of the above examples and comparative examples, as well as the aspect ratio of the fiber reinforcement and the molecular weight of the polymer binder.
  • the thickness, width, length and weight of the post-formation lithium ion battery containing the negative electrode of Table 1-1 were measured. Then, the partially formed lithium-ion battery was disassembled, and its negative electrode was tested for cohesion. Another part of the lithium-ion battery was tested for cycle performance and cycle thickness expansion rate, and the test results were recorded.
  • Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-9 were subjected to a cohesion test and a lithium ion battery comprising the negative electrode was subjected to a cycle performance test and a cycle thickness expansion rate test. The results of the test are shown in the table. 1-3.
  • the lithium ion batteries in the examples of the present application can be added to the negative electrode by adding The composite binder can effectively increase the cohesion of the negative electrode to more than 40 N/m, thereby reducing the cycle thickness expansion rate of the lithium-ion battery and improving its cycle capacity retention rate.
  • Comparative Examples 1-2 and 1-3 when any component of the composite binder is used alone as a binder, the cohesion of the negative electrode cannot reach more than 30 N/m, the cycle thickness expansion rate is high, and the cycle capacity The retention rate is low.
  • the lithium-ion batteries of the examples of the present application all have a certain cohesion, and effectively reduce the cycle thickness expansion rate, so that the cycle capacity of the lithium-ion battery is improved.
  • the retention rate remains at a high level.
  • the composite binders composed of different polymer binders and fiber reinforcements provided in this application can improve the cohesion of lithium ion batteries.
  • the copolymer of polyacrylic acid and alginic acid can improve the cohesion of the negative electrode to more than 70N/m.
  • Examples 2-1 to 2-21 and comparative examples 2-1 to 2-10 are lithium ion batteries using carbon-based materials and silicon-based materials as negative electrodes, and the negative electrode formulations are shown in Table 2-1, wherein the examples Although the types and weight ratios of polymer binders and fiber reinforcements in the binders of 2-9 and 2-13 to 2-21 are the same, other parameters of the binders such as: solid content, particle size, The aspect ratio and tensile strength of the fiber reinforcement are adjusted, please refer to Table 2-2 for details.
  • Table 2-2 shows the solid content, particle size and tensile strength of the composite binders of the above examples and comparative examples, as well as the molecular weight of the polymer binder and the length and diameter of the fiber reinforcement.
  • the thickness, width, length and weight of the post-formation lithium ion battery containing the negative electrode of Table 2-1 were measured. Then, the partially formed lithium-ion battery was disassembled, and its negative electrode was tested for cohesion. Another part of the lithium-ion battery was tested for cycle performance and cycle thickness expansion rate, and the test results were recorded.
  • the negative electrodes of Examples 2-1 to 2-21 and Comparative Examples 2-1 to 2-10 were subjected to a cohesion test and a lithium ion battery comprising the negative electrode was subjected to a cycle performance test and a cycle thickness expansion rate test. The results of the test are shown in the table. 2-3.
  • the composite binder of the present application The electrochemical device using the silicon-based material anode can also improve its cycle capacity retention rate and reduce its cycle thickness expansion rate.
  • the composite binder of the polymer binder and the fiber reinforcement provided by the present application can effectively improve the cohesion of the negative electrode, thereby reducing the cycle thickness expansion rate of the lithium ion battery and improving the Its cycle capacity retention rate.
  • the composite binder of the present application as an additive of the negative electrode, can effectively improve the cohesion of the negative electrode and suppress the volume expansion rate of the negative electrode, so as to keep the structure of the negative electrode stable.
  • the ion circulation channel of the negative electrode can be optimized, so that the safety performance and cycle performance of the electrochemical device can be significantly improved.

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Abstract

本申请涉及复合粘结剂和包含其的电化学装置及电子装置。该复合粘结剂包括：高分子粘结剂及纤维增强体，其中所述高分子粘结剂为溶液型粘结剂，其包含均聚物或共聚物，所述均聚物或所述共聚物的单体包括丙烯酸、海藻酸、丙烯腈、丙烯酰胺、乙烯醇中的至少一种。本申请采用上述复合粘结剂，能够有效的提高负极活性材料层的结构强度，使其电化学装置具有良好的循环性能及安全性能。

Description

复合粘结剂和包含其的电化学装置及电子装置 技术领域
本申请涉及储能技术领域，尤其涉及复合粘结剂及包含该复合粘结剂的电化学装置及电子装置。
背景技术
随着移动电子技术的高速发展，人们使用诸如手机、平板、笔记本电脑、无人机等的移动电子装置的频率和体验要求越来越高。因此，为电子装置提供能源的电化学装置(例如，锂离子电池)需要表现出更高的能量密度、更大的倍率、更高的安全性以及在反复充放电过程后更小的容量衰减。
电化学装置的能量密度与循环效能与其正极活性材料和负极活性材料有密切的关联。有鉴于此，人们不断的对负极活性材料做进一步的研究及改进，以追求具有更高能量密度的负极活性材料。然而，具有高能量密度的材料(例如，硅基材料)往往存在与现有电极组件结构不相匹配的问题，例如，电导性过低、受热膨胀率过高、加工性能不足等等。因此，除了对具有高能量密度的负极活性材料进行改进与替换，还需要进一步对其相关的负极添加物(例如，粘结剂和导电剂)进行改进与研究。
发明内容
本申请提供一种复合粘结剂及包含该复合粘结剂的电化学装置及电子装置以试图在至少某种程度上解决至少一个存在于相关领域中的问题。
根据本申请的一个方面，本申请提供了一种复合粘结剂，该复合粘结剂包括：高分子粘结剂及纤维增强体，其中高分子粘结剂为溶液型粘结剂，其包含均聚物或共聚物，所述均聚物或所述共聚物的单体包括丙烯酸、海藻酸、丙烯腈、丙烯酰胺、乙烯醇中的至少一种。
本申请通过采用上述复合粘结剂，能够有效的提高负极活性材料层的结构强度，使其电化学装置具有良好的循环性能及安全性能。
根据本申请的另一个方面，本申请提供了一种电化学装置，该电化学装置包含正极、隔离膜以及负极。负极包含负极集流体以及负极活性材料层，其中负极活性材料层包含硅基材料、碳基材料以及上述实施例中的复合粘结剂。
根据本申请的另一个方面，本申请提供了一种电子装置，该电子装置包含上述的电化学装置。
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
附图说明
在下文中将简要地说明为了描述本申请实施例或现有技术所必要的附图以便于描述本申请的实施例。显而易见地，下文描述中的附图仅只是本申请中的部分实施例。对本领域技术人员而言，在不需要创造性劳动的前提下，依然可以根据这些附图中所例示的结构来获得其他实施例的附图。
图1为根据本申请部分实施例的复合粘结剂的示意图。
图2为高分子粘结剂与纤维增强体在不同重量比例下混合形成的复合粘结剂的拉伸强度曲线图。
图3为多种高分子粘结剂与不同纤维增强体在同比例下混合形成的复合粘结剂的拉伸强度曲线图。
具体实施方式
本申请的实施例将会被详细的描示在下文中。在本申请说明书全文中，将相同或相似的组件以及具有相同或相似的功能的组件通过类似附图标记来表示。在此所描述的有关附图的实施例为说明性质的、图解性质的且用于提供对本申请的基本理解。本申请的实施例不应该被解释为对本申请的限制。
如本文中所使用，术语“大致”、“大体上”、“实质”及“约”用以描述及说明小的变化。当与事件或情形结合使用时，该术语可指代其中事件或情形精确发生的例子以及其中事件或情形极近似地发生的例子。举例来说，当结合数值使用时，术语可指代 小于或等于数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。举例来说，如果两个数值之间的差值小于或等于该值的平均值的±10％(例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％)，那么可认为两个数值“大体上”相同。
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于该范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
除非另外明确指明，本文使用的下述术语具有下文指出的含义。
术语“海藻酸”是指一种直链的嵌段聚糖醛酸，由均聚的α-L-吡喃古罗糖醛酸嵌段、均聚的β-D-吡喃甘露糖醛酸嵌段以及这两种糖醛酸的交聚嵌段，以1，4-糖苷键连接而成有机酸聚合物。术语“海藻酸盐类”是指海藻酸与盐类所形成的衍生物，盐类包括，但不限于，钙盐、镁盐、钠盐、钾盐、锶盐中的至少一种。
术语“聚乙烯类聚合物”是指由乙烯类单体所组成的聚合物，乙烯类单体可以是乙烯与任何取代基的官能团所组成的衍生物，其包含，但不限于，乙烯醇。例如，聚乙烯醇预期是由乙烯醇单体所组成的聚合物。
术语“聚丙烯类聚合物”是指由丙烯类单体所组成的聚合物，丙烯类单体可以是丙烯与任何取代基的官能团所组成的衍生物，其包含，但不限于，丙烯酸、丙烯腈、丙烯酰胺中的至少一种。例如，聚丙烯酸预期是由丙烯酸单体所组成的聚合物。聚丙烯腈预期 是由丙烯腈单体所组成的聚合物。聚丙烯酰胺预期是由丙烯酰胺单体所组成的聚合物。
术语“羧甲基纤维素”、“羧乙基纤维素”及“羧丙基纤维素”是分别指具有羧甲基、羧乙基及羧丙基取代基的纤维素。术语“羧甲基纤维素盐类”、“羧乙基纤维素盐类”及“羧丙基纤维素盐类”是分别指羧甲基纤维素、羧乙基纤维素及羧丙基纤维素与盐类所形成的衍生物，盐类包括，但不限于，钙盐、镁盐、钠盐、钾盐、锶盐中的至少一种。
术语“纤维”是指具有较低溶解度的固态纤维。
在电化学装置的领域中，为了追求最佳的能量密度，已尝试将传统负极活性材料中的石墨替换为具有高能量密度的负极活性材料，但是在应用此类高能量密度负极活性材料时，由于不同的材料特性还需要对其做进一步的工艺处理。举例来说，硅基材料由于理论克容量高达4200m Ah/g，是未来高体积能量密度的电化学装置(例如，锂离子电池)开发的主流负极活性材料。此类高能量密度的负极活性材料在脱嵌锂过程中存在巨大的体积变化效应(例如，大于约300％)，负极严重膨胀会造成负极与隔离膜的界面变形甚至分离，进而造成锂离子电池的循环性能降低。因此，在充放电循环过程中过大的体积膨胀不仅会造成电极组件变形降低循环性能，还容易导致锂离子电池的结构被破坏，严重影响锂离子电池的安全性。
本申请从改善负极膨胀的角度出发，研究提高负极活性材料层中负极活性材料的颗粒间的粘结能力(内聚力)来抑制负极在充电中的循环膨胀。本申请提供一种具备高粘结与高韧性性能的复合粘结剂，通过将其添加至负极活性材料中以粘结和包覆在负极活性材料的颗粒表面，形成颗粒间的桥接，从而有效提升负极的内聚力。相较于现有的水溶性粘结剂，本申请的复合粘结剂包含高分子粘结剂及纤维增强体，使得复合粘结剂具有较高的强度、韧性及耐热性。再者，由于纤维增强体具有很高的取向度和结晶度(例如，50％到70％之间)，能够有效提高复合粘结剂的拉伸强度。此外，纤维增强体的羟基与高分子粘结剂的羧基和羟基能发生化学键合或生成氢键，从而形成良好的复合结构，此复合结构能够将纤维增强体的高拉伸强度优点发挥出来，能够在充电过程中对负极活性材料起到支撑作用，降低负极在充放电循环过程中的变形程度及膨胀率，保证电化学装置的循环性能及倍率性能。
根据本申请的一个方面，本申请的实施例提供一种复合粘结剂，复合粘结剂包括：高分子粘结剂及纤维增强体。高分子粘结剂为溶液型粘结剂，其包含均聚物或共聚物， 所述均聚物或所述共聚物的单体包括丙烯酸、海藻酸、丙烯腈、丙烯酰胺、乙烯醇中的至少一种。
在一些实施例中，纤维增强体包含纤维素纤维、羧甲基纤维素纤维及其衍生物、羟乙基纤维素纤维及其衍生物、羟丙基纤维素纤维及其衍生物及聚乙烯醇纤维中的至少一种。在一些实施例中，纤维增强体由聚乙烯醇纤维组成。
在一些实施例中，高分子粘结剂的重均分子量为100kDa至10000kDa。在另一些实施例中，高分子粘结剂的重均分子量大致为，例如，约100kDa、约200kDa、约500kDa、约1000kDa、约2000kDa、约5000kDa、约8000kDa、约10000kDa或这些数值中任意两者组成的范围。
在一些实施例中，纤维增强体为呈长条形的纤维。
在一些实施例中，纤维增强体的长度为5μm至100μm。在另一些实施例中，纤维增强体的长度大致为，例如，约5μm、约10μm、约20μm、约30μm、约40μm、约50μm、约75μm、约100μm或这些数值中任意两者组成的范围。
在一些实施例中，纤维增强体的直径为0.001μm至1.0μm。在另一些实施例中，纤维增强体的直径大致为，例如，约0.001μm、约0.01μm、约0.05μm、约0.1μm、约0.2μm、约0.3μm、约0.4μm、约0.5μm、约1.0μm或这些数值中任意两者组成的范围。
术语“长度”及“直径”为简化说明纤维增强体的形貌常用参数；长度为通过扫描式电子显微镜量测纤维增强体从一端至另一端的纤维长度。直径为纤维增强体的截面的纤维直径。
在一些实施例中，纤维增强体的长度与直径的长径比为100至10000。在另一些实施例中，纤维增强体的长径比大致为，例如，约100、约200、约500、约1000、约2500、约5000、约10000或这些数值中任意两者组成的范围。
图1为根据本申请部分实施例的复合粘结剂的示意图。
如图1所示，纤维增强体20在高分子粘结剂10中依然呈长条形的固态纤维状。
在一些实施例中，复合粘结剂的固含量为1％至60％。在另一些实施例中，复合粘结剂的固含量大致为，例如，约1％、约2％、约5％、约10％、约20％、约50％、约60％或这些数值中任意两者组成的范围。
在本文中，术语“固含量”是指溶液中的所有固体的重量百分比，例如，复合粘结 剂的固含量包含“高分子粘结剂”与“纤维增强体”两种物质的固含量。本申请部分实施例所提供的复合粘结剂的固含量测试方法为将复合粘结剂在130℃至200℃下烘干，并计算干燥后的剩余固体所占的重量比例。
在一些实施例中，复合粘结剂的颗粒度Dv50为1μm至100μm。在另一些实施例中，复合粘结剂的颗粒度Dv50大致为，例如，约1μm、约5μm、约10μm、约20μm、约50μm、约100μm或这些数值中任意两者组成的范围。
在本文中，术语“颗粒度”代表样品通过激光粒度测试所得到的表征颗粒特性Dv50，其中Dv50表示材料在体积基准的颗粒分布中，从小粒径侧起、达到体积累积50％的粒径。本申请实施例所提供的颗粒度测试方法为采用Mastersizer 2000激光粒度分布测试仪分析样品的颗粒的粒度：将样品分散在100mL的分散剂(去离子水)中，使遮光度达到8～12％。随后在超声强度为40KHz及180w下对样品进行超声处理5分钟。待超声处理后，将对样品进行激光粒度分布分析，得到粒度分布数据。
根据本申请的一些实施例，复合粘结剂通过混合一定比例的高分子粘结剂(例如，聚丙烯酸，PAA)与纤维增强体(例如，聚乙烯醇纤维)，能够有效的提高拉伸强度，从而在负极活性材料的颗粒间提供良好的内聚力。如图2及3所示，采用聚丙烯酸作为高分子粘结剂，以及采用聚乙烯醇纤维作为纤维增强体所形成的复合粘结剂的拉伸强度可以达到3100MPa。在本申请的一些实施例中，复合粘结剂的拉伸强度为1000MPa至3100MPa。
在本文中，术语“拉伸强度”代表样品由均匀塑性形变过渡为局部集中塑性变形的临界值，抗拉强度即表征材料最大均匀塑性形变的抗力。本申请部分实施例提供的拉伸强度测试方法包含：将粘结剂样品装入固定面积的模具中(宽度10mm且长度100mm)，将其烘干以制备厚度为2mm至3mm的胶膜，取长度方向上中间均匀的部分以获得面积为10mm x 30mm的样品条。采用高铁拉力机(AL-3000)测试样品条的应力-应变曲线，拉伸速度为50mm/min，每次测试3组平行样品，并纪录当样品条的应力-应变曲线无法呈现均匀线行曲线时的最大应力的平均值为拉伸强度。
在一些实施例中，高分子粘结剂与纤维增强体的重量比为1：10至50：1。在另一些实施例中，高分子粘结剂与纤维增强体的重量比大致为，例如，约1：10、约1：5、约1：1、约10：1、约50：1或这些数值中任意两者组成的范围。在另一些实施例中，高分子粘结剂与纤维增强体的重量比为1：6至40：1。
在一些实施例中，本申请提供的复合粘结剂的制备方法为将固定重量比例的高分子粘结剂与纤维增强体混合均匀。应理解，本申请实施例中的复合粘结剂的制备方法，在不违背本申请的精神下，可以根据具体需要选择其他能实现本申请功能的制备方法，而不受其限制。
根据本申请的另一个方面，本申请的实施例提供一种电化学装置，电化学装置包含正极、隔离膜以及负极。负极包含负极集流体以及负极活性材料层，其中负极活性材料层包含上述实施例中的复合粘结剂。在一些实施例中，电化学装置为锂离子电池。
在一些实施例中，负极集流体可为铜箔或镍箔，然而，可以采用其他能实现本申请功能的负极集流体，而不受其限制。
负极活性材料层包含能够吸收和释放锂(Li)的负极活性材料(下文中，有时称为“能够吸收/释放锂Li的负极活性材料”)。能够吸收/释放锂(Li)的材料的例子可以包括碳基材料、金属化合物、氧化物、硫化物、锂的氮化物例如LiN3、锂金属、与锂一起形成合金的金属和聚合物材料。在一些实施例中，能够吸收/释放锂(Li)的材料中，特别具有高能量密度的材料的例子包含硅、锡、锗、锑、铋、铝的单质、合金或其化合物。
举例而言，硅的理论比比容量高达4200mAh/g,是传统石墨负极的十倍多(石墨的理论比比容量为372mAh/g)。在本申请的一些实施例中，其中负极活性材料层进一步包含硅基材料及碳基材料。
在一些实施例中，硅基材料包含单质硅、氧化硅、硅合金及硅碳中的至少一种。在一些实施例中，氧化硅为通式SiOx所代表的化合物中的至少一种，其中x＝0.5-1.5，氧化硅包含晶态、非晶态或以上二者的组合。
在一些实施例中，碳基材料包含天然石墨、人造石墨、中间相碳微球、软碳及硬碳中的至少一种。
在一些实施例中，碳基材料的重量与硅基材料的重量的比值为大于0且小于或等于99。
在一些实施例中，以负极活性材料的总重量计，复合粘结剂的重量比为1％至20％。在另一些实施例中，以负极活性材料的总重量计，复合粘结剂的重量比大致为，例如，约1％、约2％、约3％、约4％、约5％、约10％、约11％、约12％、约13％、约14％、约15％、约20％或这些数值中任意两者组成的范围。
在一些实施例中，负极活性材料层进一步包括分散剂，分散剂为可溶于水溶液中的材料，其中分散剂包含羧甲基纤维素及其盐类、羟乙基纤维素及其盐类、羟丙基纤维素及其盐类、聚乙二醇及聚乙烯吡咯烷酮中的至少一种。
在一些实施例中，以负极活性材料层的总重量计，分散剂的重量小于约2％。在另一些实施例中，以负极活性材料的总重量计，分散剂的重量小于约1％。
在一些实施例中，负极活性材料层进一步包括导电剂，其中导电剂包含导电炭黑、科琴黑、石墨烯、单壁碳纳米管、多壁碳纳米管、碳纳米纤维中的至少一种。应理解，在不违背本申请的精神下，可以根据具体需要选择其他能够实现本申请功能的导电剂，而不受其限制。
在一些实施例中，以负极活性材料层的总重量计，导电剂的重量小于约2％。在另一些实施例中，以负极活性材料的总重量计，导电剂的重量小于约1％。
在一些实施例中，正极包含正极集流体。正极集流体可以为铝箔或镍箔，然而，可以采用其他能够实现本申请功能的正极集流体，而不受其限制。
在一些实施例中，正极包含正极活性材料层。正极活性材料层包括能够吸收和释放锂(Li)的正极活性材料(下文中，有时称为“能够吸收/释放锂Li的正极活性材料”)。能够吸收/释放锂(Li)的正极活性材料的实例可以包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂、锰酸锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、磷酸铁锂、钛酸锂和富锂锰基材料中的一种或多种。
在上述正极活性材料中，钴酸锂的化学式可以为Li yCo aM1 bO 2-c，其中，M1表示选自镍(Ni)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、钇(Y)、镧(La)、锆(Zr)和硅(Si)中的至少一种，y、a、b和c值分别在以下范围内：0.8≤y≤1.2、0.8≤a≤1、0≤b≤0.2、-0.1≤c≤0.2；
在上述正极活性材料中，镍钴锰酸锂或镍钴铝酸锂的化学式可以为Li zNi dM2 eO 2-f，其中，M2表示选自钴(Co)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、锆(Zr)和硅(Si)中的至少一种，z、d、e和f值分别在以下范围内：0.8≤z≤1.2、0.3≤d≤0.98、0.02≤e≤0.7、-0.1≤f≤0.2；
在上述正极活性材料中，锰酸锂的化学式为Li uMn 2-gM 3gO 4-h，其中M3表示选自钴 (Co)、镍(Ni)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)和钨(W)中的至少一种，z、g和h值分别在以下范围内：0.8≤u≤1.2、0≤g<1.0和-0.2≤h≤0.2。
在一些实施例中，正极活性材料层能够进一步包含粘结剂及导电剂中的至少一种。应理解，本领域技术人员可以根据实际需要选择其他能够实现本申请功能的粘结剂及导电剂，而不受其限制。
在一些实施例中，隔离膜包括，但不限于，选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺和芳纶中的至少一种。举例来说，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯中的至少一种组分。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电池的稳定性。在一些实施例中，隔离膜为聚丙烯，聚丙烯与上述实施例中的高分子聚合物具有很好的亲和性，有利于提高粘结层与隔离膜的粘结力。
本申请的锂离子电池还包括电解质，电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种，电解液包括锂盐和非水溶剂。
在一些实施例中，锂盐选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB和二氟硼酸锂中的一种或多种。举例来说，锂盐选用LiPF 6，因为它可以给出高的离子导电率并改善循环特性。
非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
上述碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
上述其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯及其组合。
在一些实施例中，非水溶剂选自由碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸亚丙酯、醋酸甲酯、丙酸乙酯、氟代碳酸乙烯酯及其组合所组成的群组。
应理解，本申请实施例中的正极、负极、隔离膜以及电解质的制备方法，在不违背 本申请的精神下，可以根据具体需要选择其他能够实现本申请功能的制备方法，而不受其限制。在制造电化学装置的方法的一个实施方案中，锂离子电池的制备方法包括：将上述实施例中的负极、隔膜及正极按顺序卷绕、折叠或堆叠成电极组件，将电极组件装入例如铝塑膜中，并注入电解液，随后进行真空封装、静置、化成、整形等工序，以获得锂离子电池。
虽然上面以锂离子电池进行了举例说明，但是本领域技术人员在阅读本申请之后，能够想到由本申请的粘结层可以用于其他合适的电化学装置。这样的电化学装置包括发生电化学反应的任何装置，它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地，该电化学装置是锂二次电池，包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
本申请的一些实施例进一步提供了一种电子装置，电子装置包含本申请实施例中的电化学装置。
本申请实施例的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
具体实施例
下面列举了一些具体实施例及对比例并分别对其其负极进行内聚力测试并对其电化学装置(锂离子电池)进行循环性能测试及循环厚度膨胀率测试以更好地对本申请的技术方案进行说明。
一、测试方法
1.1内聚力测试：
在干燥房环境将以下实施例中化成后的锂离子电池拆解取得完整的负极，静置5分钟待电解液挥发干，裁剪80mm×30mm大小的负极，用高铁拉力机(AL-3000)，并设置拉伸速度为50mm/min，拉伸位移为50mm以进行内聚力测试。从以下实施例中，每组取4块锂离子电池，计算锂离子电池的负极的内聚力平均值。
1.2循环性能测试：
将以下实施例及对比例中化成后的锂离子电池置于25℃±2℃的恒温箱中静置2小时，以0.7C恒流充电至4.45V，然后以4.45V恒压充电至0.05C并静置15分钟；再以0.5C恒流放电至3.0V，此为一次充放电循环过程，记录锂离子电池首次循环的放电容量；而后按上述方法重复进行200次的充放电循环过程，并记录200次循环后的放电容量。
每组取4块锂离子电池，计算锂离子电池的容量保持率的平均值。锂离子电池的循环容量保持率＝第200次循环的放电容量(mAh)/首次循环后的放电容量(mAh)×100％。
1.3循环厚度膨胀率测试：
采用600g平板测厚仪(ELASTOCON,EV 01)测试锂离子电池的厚度。
将以下实施例及对比例的化成后锂离子电池置于25℃±2℃的恒温箱中静置2小时，以0.7C恒流充电至4.45V，然后以4.45V恒压充电至0.05C并静置15分钟，纪录满充状态下的锂离子电池厚度；再以0.5C恒流放电至3.0V，此为一次充放电循环过程，记录锂离子电池首次循环的锂离子电池厚度；而后按上述方法重复进行200次的充放电循环过程，并记录200次循环后的锂离子电池厚度。
每组取4块锂离子电池，计算锂离子电池的循环厚度膨胀率的平均值。锂离子电池的循环厚度膨胀率＝(第200次循环的锂离子电池厚度/首次循环的锂离子电池厚度-1)×100％。
二、制备方法
2.1正极的制备
将钴酸锂、导电炭黑、聚偏二氟乙烯按重量比97：1.4：1.6的比例溶于N-甲基吡咯烷酮(NMP)溶液中，形成正极浆料。采用铝箔作为正极集流体，将正极浆料涂覆于正极集流体上，经过干燥、冷压、裁切程序后得到正极。
2.2负极的制备
依照如下表1中的负极配方混合溶于去离子水中，形成负极浆料。采用铜箔作为负极集流体，将负极浆料涂覆于负极集流体上，经过干燥、冷压、裁切程序后得到负极。
2.3电解液的制备
在含水量小于10ppm的环境下，将六氟磷酸锂与非水有机溶剂(碳酸乙烯酯(EC)：碳酸二乙酯(DEC)：碳酸亚丙酯(PC)：丙酸丙酯(PP)：碳酸亚乙烯酯(VC)＝20；30；20；28；2，重量比)按重量比8：92配制以形成电解液。
2.4锂离子电池的制备
采用聚乙烯膜作为隔离膜，将上述正极、隔离膜与上述负极依顺序堆叠，使隔离膜处于正极与负极中间起到隔离的作用，然后卷绕成电极组件。随后将该电极组件装入铝塑膜包装袋中，并在80℃下脱去水分后，获得干电极组件。随后将上述电解液注入干电极组件中，经过真空封装、静置、化成、整形等工序，即完成以下各实施例和对比例的锂离子电池的制备。
三、实施例与对比例
3.1碳基材料负极
实施例1-1至实施例1-16及对比例1-1至对比例1-9为采用碳基材料作为负极的锂离子电池，其中负极配方如表1-1所示。实施例1-1、1-10与对比例1-8及1-9的粘结剂中的高分子粘结剂及纤维增强体的重量比虽然相同，但是其粘结剂的其他参数例如：固含量、颗粒度、纤维增强体的长径比以及拉伸强度有所调整，具体请参考表1-2。
表1-1
Figure PCTCN2020119509-appb-000001
Figure PCTCN2020119509-appb-000002
表1-2表示上述实施例和对比例的复合粘结剂的固含量、颗粒度和拉伸强度,以及纤维增强体的长径比和高分子粘结剂的分子量。
表1-2
Figure PCTCN2020119509-appb-000003
Figure PCTCN2020119509-appb-000004
对包含表1-1的负极的化成后锂离子电池测量其厚度、宽度、长度及重量。随后拆解部分化成后锂离子电池，对其负极进行内聚力测试，并对另一部分锂离子电池进行循环性能测试以及循环厚度膨胀率测试，并记录其测试结果。
对实施例1-1至1-16及对比例1-1至1-9的负极进行内聚力测试以及对包含该负极的锂离子电池进行循环性能测试以及循环厚度膨胀率测试，测试的结果如表1-3所示。
表1-3
Figure PCTCN2020119509-appb-000005
Figure PCTCN2020119509-appb-000006
如表1-1至1-3所示，比较实施例1-1及对比例1-1至1-3可知，在相同的重量比例组成下，本申请实施例锂离子电池通过在负极中添加复合粘结剂能够有效的提升负极的内聚力到40N/m以上，进而降低锂离子电池的循环厚度膨胀率，提高其循环容量保持率。如对比例1-2及1-3所示，复合粘结剂中的任一组分单独作为粘结剂使用时，负极内聚力都无法达到30N/m以上，循环厚度膨胀率较高，循环容量保持率较低。通过比较实施例及对比例可知，在本申请所提供的高分子粘结剂与纤维增强体比例范围之内的实施例，其具有较佳的循环容量保持率及较低的厚度膨胀率，高分子粘结剂或纤维增强体的比例过高都会导致电池的循环性能降低。
通过比较实施例1-1至1-3可知，在不同的碳基材料比例下，本申请实施例锂离子电池都具有一定的内聚力，并有效降低循环厚度膨胀率，使得锂离子电池的循环容量保持率保持在较高的水平。
通过比较实施例1-1及1-5至1-9可知，本申请所提供的不同的高分子粘结剂与纤维增强体所组成的复合粘结剂，都能够提升其锂离子电池的内聚力，尤其是聚丙烯酸及海藻酸的共聚物，能够提高负极内聚力至70N/m以上。
通过比较实施例1-1、1-15及1-16与对比例1-6及1-7可知，当负极中的复合粘结 剂的重量比过低时，会导致负极的内聚力大幅下降，进而造成循环厚度膨胀率的上升；相对的，当负极中的复合粘结剂的重量比过高时，虽然依然能够抑制负极的循环膨胀率，但是却造成电化学装置的循环容量保持率的下降，使得电化学装置的循环性能降低。
3.2硅基材料负极
实施例2-1至2-21及对比例2-1至2-10为采用碳基材料及硅基材料作为负极的锂离子电池，其中的负极配方如表2-1所示，其中实施例2-9及2-13至2-21的粘结剂中的高分子粘结剂及纤维增强体的种类及重量比虽然相同，但是其粘结剂的其他参数例如：固含量、颗粒度、纤维增强体的长径比以及拉伸强度有所调整，具体请参考表2-2。
表2-1
Figure PCTCN2020119509-appb-000007
Figure PCTCN2020119509-appb-000008
表2-2表示上述实施例和对比例的复合粘结剂的固含量、颗粒度及拉伸强度以及其高分子粘结剂的分子量与纤维增强体的长度及直径。
表2-2
Figure PCTCN2020119509-appb-000009
Figure PCTCN2020119509-appb-000010
对包含表2-1的负极的化成后锂离子电池测量其厚度、宽度、长度及重量。随后拆解部分化成后锂离子电池，对其负极进行内聚力测试，并对另一部分锂离子电池进行循环性能测试以及循环厚度膨胀率测试，并记录其测试结果。
对实施例2-1至2-21及对比例2-1至2-10的负极进行内聚力测试以及对包含该负极的锂离子电池进行循环性能测试以及循环厚度膨胀率测试，测试的结果如表2-3所示。
表2-3
Figure PCTCN2020119509-appb-000011
Figure PCTCN2020119509-appb-000012
如表2-1及2-3所示，通过比较实施例2-1至2-3及对比例2-1至2-3可知，在相同的重量比例组成下，本申请的复合粘结剂对采用含硅基材料负极的电化学装置同样能够提升其循环容量保持率并降低其循环厚度膨胀率。相较于单独添加的粘结剂，采用本申请所提供的高分子粘结剂与纤维增强体的复合粘结剂能够有效的提升负极的内聚力，进而降低锂离子电池的循环厚度膨胀率并提高其循环容量保持率。
参考表2-2及表2-3，通过比较实施例2-9、2-13、2-14及2-15与对比例2-4、2-5及2-6可知，采用的复合粘结剂的固含量在1％至60％的范围内都能有效的提高粘结剂的拉伸强度，而随著拉伸强度的增加复合粘结剂的内聚力也会提高。
通过比较实施例2-9、2-16、2-17及2-18与对比例2-7及2-8可知，采用的复合粘结剂的高分子粘结剂的分子量在100kDa至10000kDa的范围内都能有效的提高粘结剂的拉伸强度。
通过比较实施例2-9、2-19、2-20及2-21与对比例2-9及2-10可知，本申请实施例所提供的复合粘结剂能够保持一定的拉伸强度，以进一步提高包含其的负极的内聚力。
通过上述实施例的比较，可以清楚的理解本申请的复合粘结剂作为负极的添加剂，能够有效的提升负极的内聚力并抑制负极的体积膨胀率，使负极的结构保持稳定。此外，本申请的电化学装置通过限定其负极的组成比例，能够优化其负极的离子循环通道，进而使得电化学装置的安全性能及循环性能能够有显著的提升。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例“，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (11)

  1. 一种复合粘结剂，其包括：
    高分子粘结剂，其中所述高分子粘结剂为溶液型粘结剂，其包含均聚物或共聚物，所述均聚物或所述共聚物的单体包括丙烯酸、海藻酸、丙烯腈、丙烯酰胺、乙烯醇中的至少一种；以及
    纤维增强体。
  2. 根据权利要求1所述的复合粘结剂，其中所述纤维增强体包含纤维素纤维、羧甲基纤维素纤维及其衍生物、羟乙基纤维素纤维及其衍生物、羟丙基纤维素纤维及其衍生物及聚乙烯醇纤维中的至少一种，且所述纤维增强体的长度为5μm至100μm，所述纤维增强体直径为0.001μm至1.0μm，且其长径比为100至10000。
  3. 根据权利要求1所述的复合粘结剂，其中所述高分子粘结剂的重均分子量为100kDa至10000kDa。
  4. 根据权利要求1所述的复合粘结剂，其中所述高分子粘结剂与所述纤维增强体的重量比为1：10至50：1。
  5. 根据权利要求1所述的复合粘结剂，其中所述复合粘结剂为水性溶液，所述复合粘结剂的固含量为1％至60％，其中所述复合粘结剂的颗粒度Dv50为1μm至100μm。
  6. 一种电化学装置，其包括：
    正极；
    隔离膜；以及
    负极，所述负极包括：
    负极集流体；以及
    负极活性材料层，其中所述负极活性材料层包括根据权利要求1-5中任一项所述的复合粘结剂。
  7. 根据权利要求6所述的电化学装置，其中所述负极活性材料层进一步包含硅基材料及碳 基材料中的至少一种，其中所述硅基材料包含单质硅、氧化硅、硅合金及硅碳中的至少一种，且所述碳基材料包含天然石墨、人造石墨、中间相碳微球、软碳及硬碳中的至少一种。
  8. 根据权利要求6所述的电化学装置，其中以所述负极活性材料层的总重量计，所述复合粘结剂的重量比为1％至20％。
  9. 根据权利要求6至8任一项所述的电化学装置，其中所述负极活性材料层进一步包括分散剂，其中以所述负极活性材料层的总重量计，所述分散剂的重量小于2％。
  10. 根据权利要求6至8中任一项所述的电化学装置，其中所述负极活性材料层进一步包括导电剂，其中以所述负极活性材料层的总重量计，所述导电剂的重量小于2％。
  11. 一种电子装置，其包含权利要求6至10中任一项所述的电化学装置。
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