WO2025190033A1 - 一种电化学装置和电子装置 - Google Patents

一种电化学装置和电子装置

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Publication number
WO2025190033A1
WO2025190033A1 PCT/CN2025/077341 CN2025077341W WO2025190033A1 WO 2025190033 A1 WO2025190033 A1 WO 2025190033A1 CN 2025077341 W CN2025077341 W CN 2025077341W WO 2025190033 A1 WO2025190033 A1 WO 2025190033A1
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WIPO (PCT)
Prior art keywords
conductive particles
positive electrode
electrochemical device
present application
active material
Prior art date
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Pending
Application number
PCT/CN2025/077341
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English (en)
French (fr)
Inventor
刘晓欠
韩冬冬
王可飞
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Application filed by Ningde Amperex Technology Ltd filed Critical Ningde Amperex Technology Ltd
Publication of WO2025190033A1 publication Critical patent/WO2025190033A1/zh
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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 electrochemical technology, and in particular to an electrochemical device and an electronic device.
  • lithium-ion batteries typically use conductive carbon to improve the conductivity of the positive electrode.
  • conductive carbon due to the strong adsorption effect of conductive carbon, side reaction products are enriched on its surface, which manifests as an increase in the diameter of the conductive carbon, affecting the conductivity of the conductive carbon and thus the cycle performance of the lithium-ion battery.
  • the purpose of this application is to provide an electrochemical device and an electronic device to improve the cycle performance of the electrochemical device.
  • the specific technical solution is as follows:
  • a first aspect of the present application provides an electrochemical device comprising a positive electrode plate, the positive electrode plate comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode active material layer comprises conductive particles, and the conductive particles comprise at least one of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , wherein the ratio of x1:x2 ranges from 80:20 to 95:5, and the ratio of y1:y2 ranges from 85:15 to 99:1.
  • Antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 have good electrical conductivity but poor adsorption capacity, thereby improving the conductivity of the conductive particles.
  • antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 are located on at least a portion of the surface of the conductive particles, and the ratio of the coverage area of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 to the total surface area of the conductive particles is Z, where Z is ⁇ 50%.
  • the thickness of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles is 0.5 nm to 70 nm.
  • the conductivity of the conductive particles is improved, thereby improving the cycling performance of the electrochemical device.
  • the diameter of the conductive particles is d ⁇ m, 0.002 ⁇ d ⁇ 0.15, preferably 0.02 ⁇ d ⁇ 0.07.
  • the conductive particles are in the form of strings, and the length of the strings is L ⁇ m, with 0.05 ⁇ L ⁇ 5.
  • the strings of conductive particles and the control of the string length within the scope of the present application can enhance the long-range conductivity of the conductive particles, while also facilitating the storage of electrolyte between the conductive particles, increasing the ionic conductivity of the positive electrode sheet, and further improving the cycling performance of the electrochemical device.
  • the BET specific surface area of the strings of conductive particles is 150 m 2 /g to 1000 m 2 /g.
  • the conductive particles are filled with carbon, antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 , or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 .
  • This configuration allows the conductive particles to have good conductivity and improves the cycling performance of the electrochemical device.
  • the positive electrode active material layer includes a positive electrode active material, and the particle size of the positive electrode active material satisfies at least one of the following characteristics: (1) 5 ⁇ m ⁇ Dv50 ⁇ 20 ⁇ m, 25 ⁇ m ⁇ Dv99 ⁇ 50 ⁇ m; (2) the diameter of the conductive particles is d ⁇ m, 80 ⁇ Dv50/d ⁇ 6000; (3) the conductive particles are in the form of strings, and the length of the strings composed of conductive particles is L ⁇ m, 5 ⁇ Dv99/L ⁇ 1000.
  • the particle size of the positive electrode active material that satisfies at least one of the above characteristics is beneficial to the grading of the conductive particles and the positive electrode active material, improves the compaction density of the positive electrode sheet, and can enable the lithium-ion battery to have a higher energy density.
  • the weight percentage of the conductive particles is 0.1% to 3% based on the weight of the positive electrode active material layer.
  • the diameter growth rate of the conductive particles is ⁇ 15%. This indicates that the diameter growth rate of the conductive particles is small, and the conductive particles still maintain good conductivity, thus enabling the electrochemical device to have good cycling performance.
  • the second aspect of the present application provides an electronic device comprising the electrochemical device provided in the first aspect of the present application.
  • the electrochemical device provided in the first aspect of the present application has good cycle performance, so the electronic device provided in the second aspect of the present application has a long service life.
  • Antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 have good conductivity but poor adsorption capacity, thereby improving the conductivity of the conductive particles.
  • a lithium-ion battery is used as an example of an electrochemical device to explain the present application, but the electrochemical device of the present application is not limited to a lithium-ion battery.
  • a first aspect of the present application provides an electrochemical device, comprising a positive electrode plate, the positive electrode plate comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising conductive particles, the conductive particles comprising at least one of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , wherein the ratio of x1:x2 ranges from 80:20 to 95:5, and the ratio of y1:y2 ranges from 85:15 to 99:1.
  • SnO antimony-doped tin oxide
  • ZnO zinc oxide
  • x1:x2 in antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 , x1:x2 can be 80:20, 83:17, 85:15, 87:13, 90:10, 93:7, 95:5, or a range consisting of any two values therein; in aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , y1:y2 can be 85:15, 87:13, 90:10, 93:7, 95:5, 99:1, or a range consisting of any two values therein.
  • antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 have good electrical conductivity and poor adsorption capacity, which is beneficial to improving the conductivity of the conductive particles, improving the accumulation of side reaction products on the surface of the conductive particles, reducing the diameter growth rate of the conductive particles, and also facilitating the uniform distribution of the binder and conductive particles in the positive electrode sheet, thereby improving the conductivity of the positive electrode sheet and reducing the polarization of the battery cell.
  • the conductive particles include at least one of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , and regulating the values of x1:x2 and y1:y2 within the scope of this application, which is beneficial to improving the conductivity of the conductive particles and improving the cycle performance of the electrochemical device.
  • SnO antimony-doped tin oxide
  • ZnO zinc oxide
  • antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 are located on at least a portion of the surface of the conductive particles, and the ratio of the coverage area of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 to the total surface area of the conductive particles is Z, where Z is ⁇ 50%.
  • the value of Z can be 50%, 60%, 70%, 80%, 90%, 100%, or a range consisting of any two of these values.
  • the thickness of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles is 0.5 nm to 70 nm.
  • the thickness of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles can be 0.5 nm, 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, or a range consisting of any two of these values.
  • the conductivity of the conductive particles is improved and the cycle performance of the electrochemical device is improved.
  • the conductive particles are in the form of strings, and the length of the strings composed of the conductive particles is L ⁇ m, 0.05 ⁇ L ⁇ 5.
  • the length of the strings composed of the conductive particles can be 0.05 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m or a range consisting of any two of these values.
  • the conductive particles are in the form of strings and the length of the strings is regulated within the scope of the present application, which can enable the conductive particles to play a long-range conductive role and improve the conductivity of the conductive particles.
  • the conductive particles are in the form of strings, which means that a plurality of conductive particles are linked to form a string.
  • the BET specific surface area of the strings of conductive particles is between 150 m 2 /g and 1000 m 2 /g.
  • the BET specific surface area of the strings of conductive particles can be 150 m 2 /g, 300 m 2 /g, 350 m 2 /g, 400 m 2 /g, 450 m 2 /g, 500 m 2 /g, 550 m 2 /g, 600 m 2 /g, 800 m 2 /g, 900 m 2 /g, 1000 m 2 /g, or a range consisting of any two values therein.
  • the conductive particles are composed of carbon, antimony -doped tin oxide (SnO) x1 ( Sb2O3 ) x2 , or aluminum -doped zinc oxide (ZnO) y1 ( Al2O3 ) y2 .
  • This configuration allows for excellent conductivity in the conductive particles, improving the cycling performance of the electrochemical device.
  • the carbon element may include at least one of graphene, Ketjen black, or conductive carbon black (Super P).
  • the positive electrode active material layer includes a positive electrode active material, and the particle size of the positive electrode active material satisfies at least one of the following characteristics: (1) 5 ⁇ m ⁇ Dv50 ⁇ 20 ⁇ m, 25 ⁇ m ⁇ Dv99 ⁇ 50 ⁇ m; (2) the diameter of the conductive particles is d ⁇ m, 80 ⁇ Dv50/d ⁇ 6000; Dv50 is the Dv50 of the positive electrode active material, in ⁇ m; (3) the conductive particles are in the form of strings, the length of the strings composed of the conductive particles is L ⁇ m, 5 ⁇ Dv99/L ⁇ 1000, and Dv99 is the Dv99 of the positive electrode active material, in ⁇ m.
  • the weight percentage of the conductive particles is 0.1% to 3% based on the weight of the positive electrode active material layer.
  • the weight percentage of the conductive particles can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or a range consisting of any two of these values.
  • the diameter growth rate of the conductive particles is ⁇ 15%. This indicates that the diameter growth rate of the conductive particles is small, the conductive particles still maintain good conductivity, and that the electrochemical device has good cycling performance.
  • the capacity retention rate of the electrochemical device is ⁇ 80%, indicating that the electrochemical device has good cycle performance.
  • the preparation method of the conductive particles with carbon elements inside may include but is not limited to the following steps: first, a hydrocarbon substance is pyrolyzed and purified under high temperature conditions to obtain high-purity nano conductive carbon particles, and the above-mentioned hydrocarbon substance may include but is not limited to at least one of acetylene or methane.
  • Commercially available conductive carbon particles can also be used. Nano conductive carbon particles are used as a carbon source, dissolved in water with a metal salt, an oxidant, a precipitant, a surfactant, etc.
  • the preparation method of the conductive particles whose interior is antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 may include but is not limited to the following steps: dissolving metal salt, oxidant, precipitant, surfactant, etc.
  • Metal salts used to synthesize (SnO) x1 ( Sb2O3 ) x2 include tin salts and antimony salts.
  • Tin salts may include, but are not limited to, at least one of tin dichloride, tin nitrate, and tin sulfate.
  • Antimony salts may include, but are not limited to, at least one of antimony trichloride, antimony nitrate, and antimony sulfate.
  • Metal salts used to synthesize (ZnO) y1 ( Al2O3 ) y2 include zinc salts and aluminum salts.
  • Zinc salts may include, but are not limited to, at least one of zinc dichloride, zinc sulfate, and zinc acetate.
  • Aluminum salts may include, but are not limited to, at least one of aluminum trichloride, aluminum nitrate, and aluminum sulfate.
  • the aforementioned oxidant may include, but are not limited to, at least one of nitric acid and hydrogen peroxide.
  • the precipitant may include, but are not limited to, at least one of ammonium hydroxide and sodium hydroxide.
  • the aforementioned surfactant may include, but are not limited to, at least one of sodium nitrate and sodium lauryl sulfate.
  • the present application has no particular restrictions on the temperature of the reaction in the hydrothermal kettle, the pressure of the reaction in the hydrothermal kettle, the time of the reaction in the hydrothermal kettle, the calcination temperature, the calcination time, the high-temperature sintering temperature, and the high-temperature sintering time, as long as the purpose of the present application can be achieved.
  • the temperature of the reaction in the hydrothermal kettle can be 100°C to 200°C
  • the pressure of the reaction in the hydrothermal kettle can be 1MPa to 5MPa
  • the time of the reaction in the hydrothermal kettle can be 3h to 10h
  • the calcination temperature can be 130°C to 250°C
  • the calcination time can be 22h to 26h
  • the high-temperature sintering temperature can be 700°C to 1100°C
  • the high-temperature sintering time can be 1h to 5h.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode current collector can include aluminum foil or aluminum alloy foil.
  • the positive electrode active material layer of this application includes a positive electrode active material. This application does not specifically limit the type of positive electrode active material, as long as the objectives of this application can be achieved.
  • the positive electrode active material can include at least one of lithium nickel cobalt manganese oxide (NCM811, NCM622, NCM523, NCM111), lithium nickel cobalt aluminum oxide, lithium iron phosphate, a lithium-rich manganese-based material, lithium cobalt oxide ( LiCoO2 ), lithium manganese oxide, lithium iron manganese phosphate, or lithium titanate, preferably at least one of lithium nickel cobalt manganese oxide (NCM811, NCM622, NCM523, NCM111), lithium cobalt oxide ( LiCoO2 ), and lithium manganese oxide.
  • NCM811, NCM622, NCM523, NCM111 lithium nickel cobalt manganese oxide
  • LiCoO2 lithium nickel cobalt oxide
  • the mass percentage of the positive electrode active material can be 93% to 99%, for example, the mass percentage of the positive electrode active material is 93%, 94%, 95%, 96%, 97%, 98%, 99% or a range consisting of any two values therein.
  • the thickness of the positive electrode current collector and the positive electrode active material layer there is no particular restriction on the thickness of the positive electrode current collector and the positive electrode active material layer, as long as the purpose of the present application can be achieved.
  • the thickness of the positive electrode current collector is 5 ⁇ m to 20 ⁇ m, preferably 6 ⁇ m to 18 ⁇ m.
  • the thickness of the single-sided positive electrode active material layer is 30 ⁇ m to 120 ⁇ m.
  • the positive electrode active material layer can be arranged on one surface in the thickness direction of the positive electrode current collector, or on two surfaces in the thickness direction of the positive electrode current collector. It should be noted that the "surface" here can be the entire area of the positive electrode current collector or a partial area of the positive electrode current collector. There is no particular restriction in the present application, as long as the purpose of the present application can be achieved.
  • the positive electrode active material layer of the present application may further include a positive electrode conductive agent and a positive electrode binder. The present application has no particular restrictions on the positive electrode conductive agent and the positive electrode binder, as long as the purpose of the present application can be achieved.
  • the conductive agent may include at least one of graphene, carbon nanotubes, Ketjen black, graphite fiber, or conductive carbon black (Super P).
  • the mass percentage of the positive electrode conductive agent may be 0.1% to 3%, for example, the mass percentage of the positive electrode conductive agent is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or a range consisting of any two of these values.
  • the positive electrode binder may include at least one of polyacrylic acid, polyvinylidene fluoride (PVDF), polytetrafluoroethylene-hexafluoropropylene, sodium polyacrylate, nitrile rubber or polyacrylate.
  • the negative electrode current collector can include but is not limited to copper foil, copper alloy foil, nickel foil, titanium foil, foam nickel, foam copper or composite current collector, etc.
  • the negative electrode active material layer of the present application contains negative electrode active material.
  • the present application has no special restrictions on the type of negative electrode active material, as long as the purpose of the present application can be achieved.
  • the negative electrode active material may include, but is not limited to, at least one of natural graphite, artificial graphite, mesophase microcarbon beads (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO x (0 ⁇ x ⁇ 2), or metallic lithium.
  • the electrochemical device of the present application also includes an electrolyte, and the electrolyte may include a lithium salt and an organic solvent.
  • the present application does not particularly limit the type of lithium salt, as long as the purpose of the present application can be achieved.
  • the lithium salt may include but is not limited to lithium hexafluorophosphate ( LiPF6 ), lithium tetrafluoroborate ( LiBF4 ) , lithium difluorophosphate ( LiPO2F2 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalatoborate) (LiBOB) or lithium difluorooxalatoborate (LiDFOB).
  • LiPF6 lithium hexafluorophosphate
  • LiBF4 lithium tetrafluoroborate
  • LiPO2F2 lithium difluorophosphate
  • LiTFSI lithium bis(
  • the above-mentioned linear carbonate compound may include but is not limited to at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate or methylethyl carbonate.
  • the above-mentioned cyclic carbonate compound may include but is not limited to at least one of ethylene carbonate, propylene carbonate, butylene carbonate or vinylethylene carbonate.
  • the above-mentioned carboxylate compound may include but is not limited to at least one of methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, decanoic acid, valerolactone or caprolactone.
  • the above-mentioned ether compound may include but is not limited to at least one of ethylene glycol dimethyl ether, dibutyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-1-methoxyethane, 2-methyltetrahydrofuran or tetrahydrofuran.
  • the above-mentioned other organic solvents may include but are not limited to at least one of dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate or trioctyl phosphate.
  • the electrochemical device of the present application also includes a diaphragm to separate the positive electrode sheet and the negative electrode sheet, prevent internal short circuit of the electrochemical device, allow electrolyte ions to pass freely, and do not affect the electrochemical charge and discharge process.
  • the present application has no special restrictions on the diaphragm, as long as the purpose of the present application can be achieved.
  • the material of the diaphragm may include but is not limited to polyethylene (PE), polypropylene (PP), polytetrafluoroethylene-based polyolefin (PO) diaphragms, polyester films (such as polyethylene terephthalate (PET) films), cellulose films, polyimide films (PI), polyamide films (PA), spandex or aramid films, etc.
  • the type of diaphragm may include but is not limited to at least one of a woven membrane, a non-woven membrane (non-woven fabric), a microporous membrane, a composite membrane, a rolled membrane or a spun membrane, etc.
  • the diaphragm of the present application may have a porous structure, and the porous layer is provided on at least one surface of the diaphragm, and the porous layer includes inorganic particles and a binder.
  • the inorganic particles may include at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the binder may include at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the present application does not particularly limit the size of the pore size of the porous structure, as long as the purpose of the present application can be achieved, for example, the size of the pore size can be 0.01 ⁇ m to 1 ⁇ m.
  • the thickness of the diaphragm is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness can be 3 ⁇ m to 500 ⁇ m.
  • the electrochemical device of the present application also includes a packaging bag for containing the positive electrode sheet, separator, negative electrode sheet, and electrolyte, as well as other components of the electrochemical device known in the art.
  • a packaging bag for containing the positive electrode sheet, separator, negative electrode sheet, and electrolyte, as well as other components of the electrochemical device known in the art.
  • This application does not limit these other components.
  • This application does not particularly limit the packaging bag and can be any packaging bag known in the art, as long as it can achieve the purpose of this application. For example, an aluminum-plastic film packaging bag can be used.
  • the electrochemical device of the present application is not particularly limited and may include any device that undergoes an electrochemical reaction.
  • the electrochemical device may include, but is not limited to, a lithium-ion battery, a sodium-ion battery, a lithium polymer secondary battery, or a lithium-ion polymer secondary battery.
  • the preparation process of the electrochemical device of the present application is well known to those skilled in the art and is not particularly limited in the present application.
  • it may include but is not limited to the following steps: stacking the positive electrode sheet, the separator and the negative electrode sheet in order, and winding, folding and other operations as needed to obtain an electrode assembly with a wound structure, placing the electrode assembly in a packaging bag, injecting an electrolyte into the packaging bag and sealing it to obtain an electrochemical device; or stacking the positive electrode sheet, the separator and the negative electrode sheet in order, and then fixing the four corners of the entire stacked structure with tape to obtain an electrode assembly with a stacked structure, placing the electrode assembly in a packaging bag, injecting an electrolyte into the packaging bag and sealing it to obtain an electrochemical device.
  • an overcurrent protection element, a guide plate, etc. may also be placed in the packaging bag as needed to prevent pressure rise and overcharging and discharging inside the electrochemical device.
  • the second aspect of the present application provides an electronic device, which includes the electrochemical device provided by the first aspect of the present application.
  • the electrochemical device provided by the present application has good cycle performance, so the electronic device provided by the present application has a long service life.
  • the electronic device of the present application is not particularly limited and can be any electronic device known in the art.
  • the electronic device can include, but is not limited to, a laptop computer, a pen-type computer, a mobile computer, an e-book player, a portable phone, a portable fax machine, a portable copier, a portable printer, a headset, a video recorder, an LCD television, a portable cleaner, a portable CD player, a mini-disc, a transceiver, an electronic notepad, a calculator, a memory card, a portable recorder, a radio, a backup power supply, a motor, an automobile, a motorcycle, a power-assisted bicycle, a bicycle, a lighting fixture, a toy, a game console, a clock, a power tool, a flashlight, a camera, a large household battery or a lithium-ion capacitor, etc.
  • the lithium-ion battery was disassembled to obtain the positive electrode sheet, which was then soaked in dimethyl carbonate (DMC) at 25 ⁇ 5°C for 30 min and then taken out and naturally dried.
  • DMC dimethyl carbonate
  • the positive electrode obtained in (1) was observed and tested using a scanning electron microscope (instrument model: ZEISSSEM) to measure the diameter of 15 conductive particles and the length of the string composed of 15 conductive particles. The average values were recorded as the diameter d of the conductive particles and the length L of the string composed of the conductive particles.
  • the surface elements of the positive electrode were tested using EDS. The obtained Sn element content was x1, 1/2 of the Sb element content was x2, the Zn element content was y1, and 1/2 of the Al element content was y2.
  • the positive electrode sheet obtained in (1) was cut under plasma to obtain a cross-section of the positive electrode sheet.
  • the internal elements of the conductive particles and the coverage and thickness of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 /aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles were observed and tested under a scanning electron microscope at 15 locations.
  • the average value was taken and recorded as the coverage Z and thickness of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 /aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles.
  • the coverage of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 /aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 on the surface of the conductive particles was obtained by testing using statistical software.
  • the specific surface area of the conductive particles was measured using a Tristar II 3020M surface area analyzer using nitrogen adsorption. The specific testing was conducted in accordance with the national standard GB/T 19587-2017, "Determination of the Specific Surface Area of Solids by the BET Method for Gas Adsorption.”
  • the lithium-ion battery was placed at 45°C for 60 minutes, then discharged at a constant current of 0.5C to 3V and allowed to stand for 5 minutes.
  • the process in [ ] is cycled 49 times, and the battery discharge capacity is recorded as C 1 , C 2 , C 3 .... C 49 in sequence; in the 50th cycle, charge to 4.5V at a constant current of 0.5C, charge to 0.05C at a constant voltage of 4.5V, let it stand for 5 minutes, and then discharge to 3V at a constant current of 0.2C.
  • the lithium-ion battery discharge capacity is recorded as C 50 ⁇
  • the process in ⁇ is cycled 10 times, and the process in [] is cycled once.
  • the discharge capacity of the lithium-ion battery at this time is recorded as C 501 .
  • the capacity retention rate of the lithium-ion battery after 501 cycles C 501 /C 1 ⁇ 100%.
  • LiCoO2 Lithium cobalt oxide
  • PVDF polyvinylidene fluoride
  • CNTs carbon nanotubes
  • the negative electrode active materials graphite, styrene-butadiene rubber, and sodium carboxymethyl cellulose, were mixed in a mass ratio of 97.5:1.3:1.2. Deionized water was then added as a solvent to create a negative electrode slurry with a solids content of 70 wt%, which was then stirred thoroughly. The negative electrode slurry was evenly coated on one surface of a 6 ⁇ m thick copper foil, dried at 95°C, and cold pressed to produce a 120 ⁇ m thick negative electrode sheet coated on one side with the negative electrode active material layer. The negative electrode sheet was cut into 74 mm x 875 mm sheets for later use.
  • a polyethylene film with a thickness of 5 ⁇ m (supplied by Celgard) was used.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio of 30:50:20, and then lithium salt LiPF6 was added to the organic solvent to dissolve and mix evenly to obtain an electrolyte with a lithium salt concentration of 1.15 mol/L.
  • the positive electrode sheet, separator, and negative electrode sheet are stacked in order, with the separator positioned between the positive and negative electrodes to provide insulation.
  • the electrodes are then wound to form an electrode assembly.
  • the electrode assembly is then placed in an aluminum-plastic film packaging bag, dehydrated at 80°C, and then injected with the aforementioned electrolyte and packaged.
  • the lithium-ion battery is then produced through a series of processes, including formation, degassing, and shaping.
  • Example 1 Except for adjusting the parameters of the conductive particles according to Table 1 in the "Preparation of Positive Electrode Sheet", the rest is the same as Example 1.
  • the preparation of the positive electrode sheet was the same as in Example 1, except that the parameters of the conductive particles were adjusted according to Table 1, and the conductive particles were (SnO) x1 (Sb 2 O 3 ) x2 (ATO).
  • the preparation of the positive electrode sheet was the same as in Example 1, except that the parameters of the conductive particles were adjusted according to Table 1, and the conductive particles were (ZnO) y1 (Al 2 O 3 ) y2 (AZO).
  • Example 1 Except for adjusting the relevant parameters in Table 1 in the preparation of the positive electrode sheet, the rest is the same as in Example 1.
  • the conductive particles include at least one of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , and regulating the values of x1:x2 and y1:y2 within the scope of the present application is beneficial to improving the conductivity of the conductive particles, and can enable the lithium-ion battery to have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • SnO antimony-doped tin oxide
  • ZnO zinc oxide
  • the researchers of this application found that the ratio Z of the coverage area of antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 and/or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 in the conductive particles to the total surface area of the conductive particles will affect the cycle performance of the lithium-ion battery.
  • SnO antimony-doped tin oxide
  • ZnO aluminum-doped zinc oxide
  • the diameter d value of the conductive particles affects the cycle performance of the lithium-ion battery. It can be seen from Examples 1 and 17 to 19 that by regulating the diameter d value of the conductive particles within the scope of this application, it is beneficial to improve the conductivity of the conductive particles, and the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • the length L of the strings formed by the conductive particles affects the cycle performance of the lithium-ion battery. It can be seen from Examples 1 and 20 to 22 that by regulating the length L of the strings formed by the conductive particles within the scope of this application, it is beneficial to improve the conductivity of the conductive particles, and the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • the specific surface area BET of the strings composed of conductive particles will affect the cycle performance of the lithium-ion battery. From Examples 1 to 30, it can be seen that by regulating the specific surface area BET of the strings composed of conductive particles within the scope of this application, it is beneficial to improve the conductivity of the conductive particles, and the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • the researchers of this application found that the internal material of the conductive particles will affect the cycle performance of the lithium-ion battery. It can be seen from Examples 1, 4, 23 to 24 that the interior of the conductive particles is one of carbon elements, antimony-doped tin oxide (SnO) x1 (Sb 2 O 3 ) x2 , or aluminum-doped zinc oxide (ZnO) y1 (Al 2 O 3 ) y2 , which is beneficial to improving the conductivity of the conductive particles and can make the lithium-ion battery have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • SnO antimony-doped tin oxide
  • ZnO zinc oxide
  • the particle size Dv50 of the positive electrode active material affects the cycle performance of the lithium-ion battery. It can be seen from Examples 1 and 25 to 26 that by regulating the particle size Dv50 of the conductive particle positive electrode active material within the scope of this application, the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • the particle size Dv99 of the positive electrode active material affects the cycle performance of the lithium-ion battery. It can be seen from Example 1, Example 27 to Example 28 that by regulating the particle size Dv99 of the conductive particle positive electrode active material within the scope of this application, the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.
  • the researchers of this application found that the mass percentage of the conductive particles in the positive electrode active material layer affects the cycle performance of the lithium-ion battery. It can be seen from Examples 1 and 29 to 30 that by regulating the mass percentage of the conductive particles in the positive electrode active material layer within the scope of this application, the lithium-ion battery can have a lower conductive particle diameter growth rate and a higher capacity retention rate, indicating that the lithium-ion battery has good cycle performance.

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Abstract

一种电化学装置和电子装置，电化学装置包括正极极片，正极极片包括正极集流体及设置于正极集流体至少一个表面上的正极活性材料层，正极活性材料层包括导电颗粒，导电颗粒包括掺锑氧化锡(SnO) x1(Sb 2O 3) x2或掺铝氧化锌(ZnO) y1(Al 2O 3) y2中的至少一种，其中，x1:x2的比值范围为80:20到95:5，y1:y2的比值范围为85:15到99:1。掺锑氧化锡(SnO) x1(Sb 2O 3) x2和掺铝氧化锌(ZnO) y1(Al 2O 3) y2具有良好的导电性且吸附能力较差，可提高导电颗粒的导电性。通过上述设置，有利于提高导电颗粒的导电性，从而改善电化学装置的循环性能。

Description

一种电化学装置和电子装置
本申请要求于2024年3月12日提交中国专利局、申请号为202410282302.6、发明名称为“一种电化学装置和电子装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及电化学技术领域，特别是涉及一种电化学装置和电子装置。
背景技术
锂离子电池(电化学装置)具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性好等优点，广泛应用于便携式电能储存、电子设备、电动汽车等各个领域。随着锂离子电池在上述领域中的广泛应用，市场对锂离子电池的电化学性能要求越来越高。
现有技术中，锂离子电池通常会使用导电碳来提高正极极片的导电性，但是，在锂离子电池充放电过程中，由于导电碳具有较强的吸附作用，副反应产物在其表面富集，表现为导电碳的直径变大，影响导电碳的导电性，从而影响锂离子电池的循环性能。
发明内容
本申请的目的在于提供一种电化学装置和电子装置，以改善电化学装置的循环性能。具体技术方案如下：
本申请的第一方面提供了一种电化学装置，其包括正极极片，正极极片包括正极集流体及设置于正极集流体至少一个表面上的正极活性材料层，正极活性材料层包括导电颗粒，导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，其中，x1:x2的比值范围为80:20到95:5，y1:y2的比值范围为85:15到99:1。掺锑氧化锡(SnO)x1(Sb2O3)x2和掺铝氧化锌(ZnO)y1(Al2O3)y2具有良好的导电性且吸附能力较差，可提高导电颗粒的导电性。导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，并调控x1:x2和y1:y2的值在本申请的范围内，有利于提高导电颗粒的导电性，从而改善电化学装置的循环性能。
在本申请的一些实施方案中，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2位于导电颗粒的至少部分表面，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值为Z，Z≥50％。通过调控掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值Z在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度为0.5nm至70nm。通过调控掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒的直径为dμm，0.002≤d≤0.15，优选地，0.02≤d≤0.07。通过调控导电颗粒的直接在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒多颗粒呈串状物形态，导电颗粒组成的串状物长度为Lμm，0.05≤L≤5。导电颗粒呈串状物形态并调控串状物的长度在本申请的范围内，可以增加导电颗粒的长程导电作用，同时还有利于电解液在导电颗粒间的存储，提高正极极片的离子电导率，进一步改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒组成的串状物比表面积BET为150m2/g至1000m2/g。通过调控导电颗粒组成的串状物的比表面积在本申请的范围内，有利于提高导电颗粒的导电性，进一步改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒的内部为碳元素、掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2。通过上述设置，可使导电颗粒具有良好的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，正极活性材料层包括正极活性材料，正极活性材料的颗粒度满足以下特征中的至少一者：(1)5μm≤Dv50≤20μm，25μm≤Dv99≤50μm；(2)导电颗粒的直径为dμm，80≤Dv50/d≤6000；(3)导电颗粒多颗粒呈串状物形态，导电颗粒组成的串状物长度为Lμm，5≤Dv99/L≤1000。正极活性材料的颗粒粒度满足上述特征中的至少一者，均有利于导电颗粒和正极活性材料的级配，提高正极极片的压实密度，可以使锂离子电池具有较高的能量密度。
在本申请的一些实施方案中，基于正极活性材料层的质量，导电颗粒的质量百分含量为0.1％至3％。通过调控导电颗粒的质量百分含量在本申请的范围内，有利于提高正极极片的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，电化学装置在45℃下循环501周后，导电颗粒的直径增长率≤15％。说明导电颗粒的直径增长率较小，导电颗粒依旧保持良好的导电性，使电化学装置具有良好的循环性能。
本申请的第二方面提供了一种电子装置，其包括本申请第一方面提供的电化学装置。本申请第一方面提供的电化学装置具有良好的循环性能，从而本申请第二方面提供的电子装置具有较长的使用寿命。
本申请的有益效果：
本申请提供了一种电化学装置和电子装置，电化学装置包括正极极片，正极极片包括正极集流体及设置于正极集流体至少一个表面上的正极活性材料层，正极活性材料层包括导电颗粒，导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，其中，x1:x2的比值范围为80:20到95:5，y1:y2的比值范围为85:15到99:1。掺锑氧化锡(SnO)x1(Sb2O3)x2和掺铝氧化锌(ZnO)y1(Al2O3)y2具有良好的导电性且吸附能力较差，可提高导电颗粒的导电性。导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，并调控x1:x2和y1:y2的值在本申请的范围内，有利于提高导电颗粒的导电性，从而改善电化学装置的循环性能。
当然，实施本申请的任一产品或方法并不一定需要同时达到以上所述的所有优点。
具体实施方式
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。本领域技术人员基于本申请所获得的所有其他实施例，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
本申请的第一方面提供了一种电化学装置，其包括正极极片，正极极片包括正极集流体及设置于正极集流体至少一个表面上的正极活性材料层，正极活性材料层包括导电颗粒，导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，其中，x1:x2的比值范围为80:20到95:5，y1:y2的比值范围为85:15到99:1。例如掺锑氧化锡(SnO)x1(Sb2O3)x2中x1:x2可以为80:20、83:17、85:15、87:13、90:10、93:7、95:5或为其中任意两个数值组成的范围；掺铝氧化锌(ZnO)y1(Al2O3)y2中y1:y2可以为85:15、87:13、90:10、93:7、95:5、99:1或为其中任意两个数值组成的范围。
本申请研究人员发现，掺锑氧化锡(SnO)x1(Sb2O3)x2和掺铝氧化锌(ZnO)y1(Al2O3)y2具有良好的导电性，且吸附能力较差，有利于提高导电颗粒的导电性，有利于改善副反应产物在导电颗粒表面的堆积，降低导电颗粒的直径增长率，也有利于粘结剂和导电颗粒等在正极极片中均匀分布，从而有利于提高正极极片的导电性，降低电芯极化。导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，并调控x1:x2和y1:y2的值在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2位于导电颗粒的至少部分表面，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值为Z，Z≥50％。例如Z的值可以为50％、60％、70％、80％、90％、100％或为其中任意两个数值组成的范围。通过调控掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值Z在本申请的范围内，有利于提高导电颗粒的导电性，有利于改善副反应产物在导电颗粒表面的堆积，降低电芯极化，改善电化学装置的循环性能。
在本申请的一些实施方案中，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度为0.5nm至70nm。例如掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度可以为0.5nm、1nm、10nm、20nm、30nm、40nm、50nm、60nm、70nm或为其中任意两个数值组成的范围。通过调控掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒的直径为dμm，0.002≤d≤0.15，优选为0.02≤d≤0.07。例如导电颗粒的直径可以为0.002μm、0.01μm、0.02μm、0.03μm、0.04μm、0.05μm、0.06μm、0.07μm、0.08μm、0.09μm、0.1μm、0.12μm、0.14μm、0.15μm或为其中任意两个数值组成的范围。通过调控导电颗粒的直接在本申请的范围内，有利于提高导电颗粒的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒多颗粒呈串状物形态，导电颗粒组成的串状物长度为Lμm，0.05≤L≤5。例如导电颗粒组成的串状物长度可以为0.05μm、0.5μm、1μm、2μm、3μm、4μm、5μm或为其中任意两个数值组成的范围。导电颗粒呈串状物形态并调控串状物的长度在本申请的范围内，可以使导电颗粒发挥长程导电作用，提高导电颗粒的导电性，同时还有利于电解液在导电颗粒间的存储，有利于活性金属离子(例如Li+)的传输，提高正极极片的离子电导率，进一步改善电化学装置的循环性能。在本申请中，导电颗粒呈串状物形态是指多个导电颗粒之间链接形成串状物。
在本申请的一些实施方案中，导电颗粒组成的串状物比表面积BET为150m2/g至1000m2/g，例如导电颗粒组成的串状物比表面积BET可以为150m2/g、300m2/g、350m2/g、400m2/g、450m2/g、500m2/g、550m2/g、600m2/g、800m2/g、900m2/g、1000m2/g或为其中任意两个数值组成的范围。通过调控导电颗粒组成的串状物的比表面积在本申请的范围内，有利于提高导电颗粒的导电性，进一步改善电化学装置的循环性能。
在本申请的一些实施方案中，导电颗粒的内部为碳元素、掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2。通过上述设置，可使导电颗粒具有良好的导电性，改善电化学装置的循环性能。所述碳元素包括石墨烯、科琴黑或导电炭黑(Super P)中的至少一种。
在本申请的一些实施方案中，正极活性材料层包括正极活性材料，正极活性材料的颗粒度满足以下特征中的至少一者：(1)5μm≤Dv50≤20μm，25μm≤Dv99≤50μm；(2)导电颗粒的直径为dμm，80≤Dv50/d≤6000；Dv50为正极活性材料的Dv50，单位为μm；(3)导电颗粒多颗粒呈串状物形态，导电颗粒组成的串状物长度为Lμm，5≤Dv99/L≤1000，Dv99为正极活性材料的Dv99，单位为μm。正极活性材料的颗粒粒度满足上述特征中的至少一者，均有利于导电颗粒和正极活性材料的级配，提高正极极片的压实密度，可以使锂离子电池具有较高的能量密度，且有利于发挥导电颗粒导电性，改善锂离子电池的循环性能。“Dv50”是指在材料的体积基准的粒度分布中，从小粒径测起，到达体积累积50％的粒径为Dv50；“Dv99”是指在材料的体积基准的粒度分布中，从小粒径测起，到达体积累积99％的粒径为Dv99。
在本申请的一些实施方案中，基于正极活性材料层的质量，导电颗粒的质量百分含量为0.1％至3％。例如导电颗粒的质量百分含量可以为0.1％、0.5％、1％、1.5％、2％、2.5％、3％或为其中任意两个数值组成的范围。通过调控导电颗粒的质量百分含量在本申请的范围内，有利于提高正极极片的导电性，改善电化学装置的循环性能。
在本申请的一些实施方案中，电化学装置在45℃下循环501周后，导电颗粒的直径增长率≤15％。说明导电颗粒的直径增长率较小，导电颗粒依旧保持良好的导电性，说明电化学装置具有良好的循环性能。
在本申请的一些实施方案中，电化学装置在45℃下循环501周后，电化学装置的容量保持率≥80％。说明电化学装置具有良好的循环性能。
本申请对导电颗粒的制备方法没有特别限定，只要能够实现本申请的目的即可。例如导电颗粒内部为碳元素的制备方法可以包括但不限于以下步骤：首先将烃类物质在高温条件下进行热解并提纯得到高纯度的纳米导电碳颗粒，上述烃类物质可以包括但不限于乙炔或甲烷中的至少一种。也可以采用市售的导电碳颗粒。将纳米导电碳颗粒作为碳源，与金属盐、氧化剂、沉淀剂、表面活性剂等溶于水中形成水溶液，将水溶液转移至水热釜中，密封，使其在一定温度和压强下反应一段时间，再经过过滤、洗涤、煅烧，得到内部为碳元素的导电颗粒，再经过高温烧结，得到串状物形态的导电颗粒。导电颗粒内部为掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2的制备方法可以包括但不限于以下步骤：将金属盐、氧化剂、沉淀剂、表面活性剂等溶于水中形成水溶液，将水溶液转移至水热釜中，密封，使其在一定温度和压强下反应一段时间，再经过过滤、洗涤、煅烧，得到内部为掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2的导电颗粒，再经过高温烧结，得到串状物形态的导电颗粒。
合成(SnO)x1(Sb2O3)x2的金属盐包括锡盐和锑盐，锡盐可以包括但不限于二氯化锡、硝酸锡、硫酸锡中的至少一种，锑盐可以包括但不限于三氯化锑、硝酸锑、硫酸锑中的至少一种。合成(ZnO)y1(Al2O3)y2的金属盐包括锌盐和铝盐，锌盐可以包括但不限于锌二氯化锌、硫酸锌、醋酸锌中的至少一种，铝盐可以包括但不限于三氯化铝、硝酸铝、硫酸铝中的至少一种。上述氧化剂可以包括但不限于硝酸、过氧化氢中的至少一种，沉淀剂可以包括但不限于氢氧化铵、氢氧化钠中的至少一种，上述表面活性剂可以包括但不限于硝酸钠、十二烷基硫酸钠中的至少一种。
本申请对上述在水热釜中反应的温度、在水热釜中反应的压强、在水热釜中反应的时间、煅烧温度、煅烧时间、高温烧结温度、高温烧结时间没有特别限制，只要能实现本申请的目的即可，例如在水热釜中反应的温度可以为100℃至200℃、在水热釜中反应的压强可以为1MPa至5MPa、在水热釜中反应的时间可以为3h至10h、煅烧温度可以为130℃至250℃、煅烧时间可以为22h至26h、高温烧结温度可以为700℃至1100℃、高温烧结时间可以为1h至5h。
本申请对正极极片没有特别限制，只要能够实现本申请目的即可。例如，正极极片包含正极集流体和设置在正极集流体至少一个表上的正极活性材料层。本申请对正极集流体没有特别限制，只要能够实现本申请目的即可。例如，正极集流体可以包含铝箔或铝合金箔等。本申请的正极活性材料层包含正极活性材料。本申请对正极活性材料的种类没有特别限制，只要能够实现本申请目的即可。例如正极活性材料可以包含镍钴锰酸锂(NCM811、NCM622、NCM523、NCM111)、镍钴铝酸锂、磷酸铁锂、富锂锰基材料、钴酸锂(LiCoO2)、锰酸锂、磷酸锰铁锂或钛酸锂等中的至少一种，优选为镍钴锰酸锂(NCM811、NCM622、NCM523、NCM111)、钴酸锂(LiCoO2)、锰酸锂中的至少一种。基于正极活性材料层的质量，正极活性材料的质量百分含量可以为93％至99％，例如正极活性材料的质量百分含量为93％、94％、95％、96％、97％、98％、99％或为其中任意两个数值组成的范围。在本申请中，对正极集流体和正极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，正极集流体的厚度为5μm至20μm，优选为6μm至18μm。单面正极活性材料层的厚度为30μm至120μm。在本申请中，正极活性材料层可以设置于正极集流体厚度方向上的一个表面上，也可以设置于正极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是正极集流体的全部区域，也可以是正极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。本申请的正极活性材料层还可以包含正极导电剂和正极粘结剂，本申请对正极导电剂和正极粘结剂没有特别限制，只要能够实现本申请目的即可。例如，导电剂可以包括石墨烯、碳纳米管、科琴黑、石墨纤维或导电炭黑(Super P)中的至少一种，基于正极活性材料层的质量，正极导电剂的质量百分含量可以为0.1％至3％，例如正极导电剂的质量百分含量为0.1％、0.5％、1％、1.5％、2％、2.5％、3％或为其中任意两个数值组成的范围。正极粘结剂可以包括聚丙烯酸、聚偏氟乙烯(PVDF)、聚四氟乙烯-六氟丙烯、聚丙烯酸钠、丁腈橡胶或聚丙烯酸脂中的至少一种，基于正极活性材料层的质量，正极粘结剂的质量百分含量可以为0.5％至4％，例如正极粘结剂的质量百分含量为0.5％、0.8％、1％、1.5％、2％、2.5％、3％、3.5％、4％或为其中任意两个数值组成的范围。
本申请对负极极片没有特别限制，只要能够实现本申请目的即可。例如，负极极片包含负极集流体和设置在负极集流体至少一个表面上的负极活性材料层。在本申请中，负极活性材料层可以设置于负极集流体厚度方向上的一个表面上，也可以设置于负极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是负极集流体的全部区域，也可以是负极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。本申请对负极集流体没有特别限制，只要能够实现本申请目的即可。例如，负极集流体可以包括但不限于铜箔、铜合金箔、镍箔、钛箔、泡沫镍、泡沫铜或复合集流体等。本申请的负极活性材料层包含负极活性材料。本申请对负极活性材料的种类没有特别限制，只要能够实现本申请目的即可。例如，负极活性材料可以包括但不限于天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、硅-碳复合物、SiOx(0<x≤2)或金属锂等中的至少一种。在本申请中，对负极集流体和负极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，负极集流体的厚度为4μm至12μm，单面负极活性材料层的厚度为30μm至130μm。本申请的负极活性材料层还可以包含导电剂和粘结剂。本申请对导电剂和粘结剂没有特别限制，只要能够实现本申请目的即可。例如，导电剂可以包括导电炭黑(Super P)、碳纳米管(CNTs)、碳纳米纤维、石墨纤维、科琴黑、乙炔黑、天然石墨、人造石墨、鳞片石墨或石墨烯等中的至少一种。粘结剂可以包括聚丙烯酸、聚丙烯醇、聚丙烯酸脂、聚丙烯酸钠、聚丙烯酸钾、聚丙烯酸锂、聚酰亚胺、聚酰胺酰亚胺、丁腈橡胶、丁苯橡胶(SBR)、聚乙烯醇(PVA)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚四氟乙烯-六氟丙烯、聚乙烯醇缩丁醛(PVB)、水性丙烯酸树脂、羧甲基纤维素(CMC)或羧甲基纤维素钠(CMC-Na)等中的至少一种。
本申请的电化学装置还包括电解液，电解液可以包括锂盐和有机溶剂。本申请对锂盐的种类没有特别限制，只要能实现本申请的目的即可，例如锂盐可以包括但不限于六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、二氟磷酸锂(LiPO2F2)、双三氟甲烷磺酰亚胺锂(LiTFSI)、双(氟磺酰)亚胺锂(LiFSI)、双草酸硼酸锂(LiBOB)或二氟草酸硼酸锂(LiDFOB)中的至少一种。本申请对锂盐在电解液中的含量不做限定，只要能实现本申请的目的即可。本申请对上述有机溶剂的种类没有特别限制，只要能实现本申请的目的即可，例如可以包括但不限于碳酸酯化合物、羧酸酯化合物、醚化合物或其它有机溶剂中的至少一种。上述碳酸酯化合物可以包括但不限于链状碳酸酯化合物或环状碳酸酯化合物中的至少一种。上述链状碳酸酯化合物可以包括但不限于碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯或碳酸甲乙酯中的至少一种。上述环状碳酸酯化合物可以包括但不限于碳酸乙烯酯、碳酸丙烯酯、碳酸亚丁酯或碳酸乙烯亚乙酯中的至少一种。上述羧酸酯化合物可以包括但不限于甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯或己内酯中的至少一种。上述醚化合物可以包括但不限于乙二醇二甲醚、二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、1-乙氧基-1-甲氧基乙烷、2-甲基四氢呋喃或四氢呋喃中的至少一种。上述其它有机溶剂可以包括但不限于二甲亚砜、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、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯或磷酸三辛酯中的至少一种。
本申请的电化学装置还包括隔膜，用以分隔正极极片和负极极片，防止电化学装置内部短路，允许电解质离子自由通过，且不影响电化学充放电过程的进行。本申请对隔膜没有特别限制，只要能够实现本申请目的即可，例如隔膜的材料可以包括但不限于聚乙烯(PE)、聚丙烯(PP)、聚四氟乙烯为主的聚烯烃(PO)类隔膜、聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)、氨纶或芳纶膜等中的至少一种。隔膜的类型可以包括但不限于织造膜、非织造膜(无纺布)、微孔膜、复合膜、碾压膜或纺丝膜等中的至少一种。本申请的隔膜可以具有多孔结构，多孔层设置在隔膜的至少一个表面上，多孔层包括无机颗粒和粘结剂，无机颗粒可以包括氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚乙烯吡咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。本申请对多孔结构的孔径的尺寸没有特别限制，只要能实现本申请的目的即可，例如，孔径的尺寸可以为0.01μm至1μm。在本申请中，隔膜的厚度没有特别限制，只要能实现本申请的目的即可，例如厚度可以为3μm至500μm。
本申请的电化学装置还包括包装袋，用于容纳正极极片、隔膜、负极极片和电解液，以及电化学装置中本领域已知的其它部件，本申请对上述其它部件不做限定。本申请对包装袋没有特别限制，可以为本领域公知的包装袋，只要能够实现本申请目的即可。例如，可采用铝塑膜包装袋。
本申请的电化学装置没有特别限制，其可以包括发生电化学反应的任何装置。在本申请的一种实施方案中，电化学装置可以包括但不限于：锂离子电池、钠离子电池、锂聚合物二次电池或锂离子聚合物二次电池等。
本申请的电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制，例如，可以包括但不限于以下步骤：将正极极片、隔膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的电极组件，将电极组件放入包装袋内，将电解液注入包装袋并封口，得到电化学装置；或者，将正极极片、隔膜和负极极片按顺序堆叠，然后用胶带将整个叠片结构的四个角固定好得到叠片结构的电极组件，将电极组件置入包装袋内，将电解液注入包装袋并封口，得到电化学装置。此外，也可以根据需要将防过电流元件、导板等置于包装袋中，从而防止电化学装置内部的压力上升、过充放电。
本申请的第二方面提供一种电子装置，其包括本申请第一方面提供的电化学装置。本申请提供的电化学装置具有良好的循环性能，从而本申请提供的电子装置具有较长的使用寿命。
本申请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、家庭用大型蓄电池或锂离子电容器等。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“份”、“％”为质量基准。
测试方法和设备：
导电颗粒各特征量的测试
(1)将锂离子电池拆解，得到正极极片，将正极极片用碳酸二甲酯(DMC)在25±5℃环境下浸泡30min后，取出自然晾干。
(2)将(1)中所得的正极极片，使用扫描电子显微镜(仪器型号为ZEISSSEM)，观察并测试15个导电颗粒的直径及15个导电颗粒组成的串状物长度，取平均值，记为导电颗粒的直径d和导电颗粒组成的串状物长度L的值。使用EDS测试正极极片的表面元素，所得Sn元素含量即为x1，Sb元素含量的1/2即为x2，Zn元素含量即为y1，Al元素含量的1/2即为y2。
(3)将(1)中所得的正极极片在等离子体下切割，得到正极极片的横截面，在扫描电子显微镜下观察并测试15个位置处导电颗粒的内部元素及掺锑氧化锡(SnO)x1(Sb2O3)x2/掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的覆盖率和厚度，取平均值，记为掺锑氧化锡(SnO)x1(Sb2O3)x2/掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的覆盖率Z和厚度的值。掺锑氧化锡(SnO)x1(Sb2O3)x2/掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的覆盖率是使用统计软件进行测试得到的结果。
导电颗粒比表面积BET的测试
使用比表面积分析仪(TristarⅡ3020M)，通过氮吸附法对导电颗粒进行比表面积测试。其中，具体的测试依据国家标准GB/T 19587-2017《气体吸附BET法测定固态物质比表面积》进行。
正极活性材料颗粒度的测试
(1)将锂离子电池拆解，得到正极极片，将正极极片用碳酸二甲酯(DMC)在25±5℃环境下浸泡30min后，取出自然晾干。
(2)将(1)所得的正极极片置于浓硫酸中进行腐蚀，剩余颗粒即为正极活性材料。
(3)将(2)中所得的正极活性材料颗粒使用去离子水清洗并搅拌分散后，使用马尔文激光粒度仪进行测试，得到正极活性材料的Dv50和Dv99。
循环性能的测试
将锂离子电池置于45℃环境下静置60min，再以0.5C恒定电流放电至3V，静置5min。
{【以1.5C恒定电流充电至4.5V，再以恒定电压4.5V充电至0.05C，静置5min，然后以0.7C恒定电流放电至3V，静置5min】
循环【】中的流程49次，电池放电容量依次记录为C1、C2、C3….C49；第50周以0.5C恒定电流充电至4.5V，以4.5V恒定电压充电至0.05C，静置5min，再以0.2C恒定电流放电至3V，记录锂离子电池放电容量C50}
循环{}中的流程10次，再循环【】中的流程1次，记录此时锂离电池的放电容量为C501，锂离子电池循环501周后的容量保持率＝C501/C1×100％。
导电颗粒直径增长率测试
拆解未使用的锂离子电池，取出正极极片，用碳酸二甲酯(DMC)清洗后，使用扫描电子显微镜(仪器型号为ZEISSSEM)，观察并测试50颗导电颗粒的直径，计算平均值，记为d0；取相同条件下的锂离子电池进行上述循环性能的测试，将在45℃条件下循环501周后的锂离子电池进行拆解，取出正极极片，用DMC清洗后，使用扫描电子显微镜观察测试50颗导电颗粒的直径，计算平均值，记为d501，导电颗粒直径增长率＝[(d501-d0)/d0]×100％。
实施例1
<正极极片的制备>
将正极活性材料钴酸锂(LiCoO2)、正极粘结剂聚偏氟乙烯(PVDF)、导电颗粒、正极导电剂碳纳米管(CNT)按照质量比97.8:1.2:0.5:0.5进行混合，其中，正极活性材料的Dv50为12μm，正极活性材料的Dv99为30μm，导电颗粒直径d为0.03μm，导电颗粒串状物长度L为1μm，导电颗粒串状物的BET为453m2/g，(SnO)x1(Sb2O3)x2在导电颗粒表面的厚度为6nm，其中x1:x2＝90:10。然后加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成固含量为75wt％的浆料，并搅拌均匀。将正极浆料均匀涂覆在厚度为10μm的正极集流体铝箔的一个表面上，110℃条件下烘干，得到正极活性物质层厚度为60μm的单面涂布正极活性物质的正极极片。之后，在该正极极片的另一个表面上重复以上步骤，即得到双面涂布正极活性物质的正极极片。涂布完成后，将正极极片冷压，裁切成规格为74mm×867mm的片材待用。
<负极极片的制备>
将负极活性材料石墨、丁苯橡胶、羧甲基纤维素钠按质量比97.5:1.3:1.2进行混合，然后加入去离子水作为溶剂，调配成固含量为70wt％的负极浆料，并搅拌均匀。将负极浆料均匀涂布在厚度为6μm的铜箔的一个表面上，95℃条件下烘干，冷压后得到厚度为120μm单面涂布负极活性材料层的负极极片。将负极极片裁切成74mm×875mm的规格的片材待用。
<隔膜的制备>
采用厚度为5μm的聚乙烯薄膜(Celgard公司提供)。
<电解液的制备>
在干燥氩气气氛手套箱中，将有机溶剂碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)以质量比30:50:20混合，然后向有机溶剂中加入锂盐LiPF6溶解并混合均匀，得到锂盐的浓度为1.15mol/L的电解液。
<锂离子电池的制备>
将正极极片、隔离膜、负极极片按顺序依次叠好，使隔离膜处于正极极片和负极极片中间起到隔离的作用，并卷绕得到电极组件。将电极组件置于包装袋铝塑膜中，在80℃环境下脱去水分后，注入上述电解液并封装，经过化成、脱气、整形等工艺流程得到锂离子电池。
实施例2至实施例22
除了<正极极片的制备>按表1调整导电颗粒的参数以外，其余与实施例1相同。
实施例23
除了<正极极片的制备>按表1调整导电颗粒的参数，导电颗粒为(SnO)x1(Sb2O3)x2(ATO)以外，其余与实施例1相同。
实施例24
除了<正极极片的制备>按表1调整导电颗粒的参数，导电颗粒为(ZnO)y1(Al2O3)y2(AZO)以外，其余与实施例1相同。
实施例25至实施例28
除了<正极极片的制备>按表1调整相关参数以外，其余与实施例1相同。
实施例29至实施例30
除了<正极极片的制备>中按表1调整导电颗粒的质量百分含量，正极活性材料的质量百分含量随之改变以外，其余与实施例1相同。
对比例1
除了<正极极片的制备>中，导电颗粒使用导电碳以外，其余与实施例1相同。

本申请研究人员发现，导电颗粒中掺锑氧化锡(SnO)x1(Sb2O3)x2中x1:x2和掺铝氧化锌(ZnO)y1(Al2O3)y2中y1:y2的值会影响锂离子电池的循环性能，从实施例1至实施例6、对比例1可以看出，导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，并调控x1:x2和y1:y2的值在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，导电颗粒中掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值Z会影响锂离电池的循环性能，从
实施例1、实施例4、实施例7至实施例10可以看出，通过调控导电颗粒中掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值Z在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度会影响锂离子电池的循环性能，从实施例1、实施例4、实施例11至实施例13、实施例14至实施例16可以看出，通过调控掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在导电颗粒表面的厚度在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，导电颗粒的直径d值会影响锂离子电池的循环性能，从实施例1、实施例17至实施例19可以看出，通过调控导电颗粒的直径d值在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，导电颗粒形成的串状物的长度L会影响锂离子电池的循环性能，从实施例1、实施例20至实施例22可以看出，通过调控导电颗粒形成的串状物的长度L在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，导电颗粒组成的串状物比表面积BET会影响锂离子电池的循环性能，从实施例1至实施例30可以看出，通过调控导电颗粒组成的串状物比表面积BET在本申请的范围内，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，导电颗粒的内部物质会影响锂离子电池的循环性能，从实施例1、实施例4、实施例23至实施例24可以看出，导电颗粒的内部为碳元素、掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的一种，有利于提高导电颗粒的导电性，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，正极活性材料的颗粒度Dv50会影响锂离子电池的循环性能，从实施例1、实施例25至实施例26可以看出，通过调控导电颗粒正极活性材料的颗粒度Dv50在本申请的范围内，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，正极活性材料的颗粒度Dv99会影响锂离子电池的循环性能，从实施例1、实施例27至实施例28可以看出，通过调控导电颗粒正极活性材料的颗粒度Dv99在本申请的范围内，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
本申请研究人员发现，正极活性材料层中导电颗粒的质量百分含量会影响锂离子电池的循环性能，从实施例1、实施例29至实施例30可以看出，通过调控正极活性材料层中导电颗粒的质量百分含量在本申请的范围内，可以使锂离子电池具有较低的导电颗粒直径增长率和较高的容量保持率，说明锂离子电池具有良好的循环性能。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (11)

  1. 一种电化学装置，其包括正极极片，所述正极极片包括正极集流体及设置于正极集流体至少一个表面上的正极活性材料层，所述正极活性材料层包括导电颗粒，所述导电颗粒包括掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2中的至少一种，其中，x1:x2的比值范围为80:20到95:5，y1:y2的比值范围为85:15到99:1。
  2. 根据权利要求1所述的电化学装置，其中，所述掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2位于所述导电颗粒的至少部分表面，所述掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2的覆盖面积和导电颗粒总表面积的比值为Z，Z≥50％。
  3. 根据权利要求1所述的电化学装置，其中，所述掺锑氧化锡(SnO)x1(Sb2O3)x2和/或掺铝氧化锌(ZnO)y1(Al2O3)y2在所述导电颗粒表面的厚度为0.5nm至70nm。
  4. 根据权利要求1所述的电化学装置，其中，所述导电颗粒的直径为dμm，0.002≤d≤0.15。
  5. 根据权利要求1所述的电化学装置，其中，所述导电颗粒的直径为dμm，0.02≤d≤0.07。
  6. 根据权利要求1所述的电化学装置，其中，所述导电颗粒多颗粒呈串状物形态，所述导电颗粒组成的串状物长度为Lμm，0.05≤L≤5。
  7. 根据权利要求6所述的电化学装置，其中，所述导电颗粒组成的串状物比表面积BET为150m2/g至1000m2/g。
  8. 根据权利要求1所述的电化学装置，其中，所述导电颗粒的内部为碳元素、掺锑氧化锡(SnO)x1(Sb2O3)x2或掺铝氧化锌(ZnO)y1(Al2O3)y2。
  9. 根据权利要求1所述的电化学装置，其中，所述正极活性材料层包括正极活性材料，所述正极活性材料的颗粒度满足以下特征中的至少一者：
    (1)5μm≤Dv50≤20μm，25μm≤Dv99≤50μm；
    (2)所述导电颗粒的直径为dμm，80≤Dv50/d≤6000；
    (3)所述导电颗粒多颗粒呈串状物形态，所述导电颗粒组成的串状物长度为Lμm，5≤Dv99/L≤1000。
  10. 根据权利要求1所述的电化学装置，其中，基于所述正极活性材料层的质量，所述导电颗粒的质量百分含量为0.1％至3％。
  11. 一种电子装置，其包括权利要求1至10中任一项所述的电化学装置。
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