WO2023230954A1 - 二次电池、电池模块、电池包及用电装置 - Google Patents

二次电池、电池模块、电池包及用电装置 Download PDF

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WO2023230954A1
WO2023230954A1 PCT/CN2022/096609 CN2022096609W WO2023230954A1 WO 2023230954 A1 WO2023230954 A1 WO 2023230954A1 CN 2022096609 W CN2022096609 W CN 2022096609W WO 2023230954 A1 WO2023230954 A1 WO 2023230954A1
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negative electrode
lithium
secondary battery
battery
electrolyte
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PCT/CN2022/096609
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English (en)
French (fr)
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张翠平
韩昌隆
范朋
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宁德时代新能源科技股份有限公司
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Priority to KR1020247006078A priority Critical patent/KR20240032150A/ko
Priority to EP22942954.3A priority patent/EP4333149A1/en
Priority to PCT/CN2022/096609 priority patent/WO2023230954A1/zh
Priority to US18/527,410 priority patent/US20240105942A1/en
Publication of WO2023230954A1 publication Critical patent/WO2023230954A1/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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 batteries, and in particular, to a secondary battery, a battery module, a battery pack and an electrical device.
  • Secondary batteries have the advantages of reliable working performance, no pollution, and no memory effect, so they are widely used. For example, as environmental protection issues become more and more important and new energy vehicles become more popular, the demand for power secondary batteries will grow explosively. However, as the application range of secondary batteries becomes more and more extensive, severe challenges are also posed to the performance of secondary batteries.
  • This application was made in view of the above-mentioned problems, and its purpose is to provide a secondary battery, a battery module, a battery pack, and a power consumption device, and the secondary battery has excellent fast charging performance.
  • the first aspect of the present application is to provide a secondary battery, which includes: an electrode assembly and an electrolyte for infiltrating the electrode assembly; wherein the electrode assembly includes a negative electrode plate, a separator and a Positive electrode piece, the negative electrode piece includes a negative electrode current collector and a negative electrode material layer located on at least one surface of the negative electrode current collector.
  • the tortuosity of the negative electrode piece is ⁇ , then ⁇ satisfies the following formula I,
  • ⁇ is the porosity of the negative electrode material layer
  • ⁇ is the Bruggeman index of the negative electrode material
  • the secondary battery can obtain excellent fast charging characteristics and suppress lithium deposition in the negative electrode.
  • the ⁇ satisfies: 2.3 ⁇ 7.
  • the ⁇ ranges from 8 mS/cm to 14 mS/cm.
  • the conductivity ⁇ of the electrolyte is within the above range, the kinetic properties of the electrolyte can be improved, thereby further improving the fast charging characteristics of the secondary battery.
  • the porosity ⁇ of the negative electrode material layer is 25% to 45%.
  • the dynamic properties of the negative electrode material can be improved, thereby further improving the fast charging characteristics of the secondary battery.
  • the negative electrode material is graphite, and the ⁇ ranges from 1.5 to 2.2. As a result, the tortuosity of the negative electrode piece can be estimated more accurately.
  • the electrolyte includes cyclic ester, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, methyl acetate, methyl formate, ethyl formate, methyl propionate , propyl formate, ethyl propionate, and at least one of propyl acetate, and the cyclic ester includes at least one of ethylene carbonate and propylene carbonate. This makes it possible to easily adjust the conductivity of the electrolyte solution.
  • the lithium salt of the electrolyte contains at least one of lithium hexafluorophosphate (LiPF 6 ) and fluorine-containing lithium sulfonyl imide, and the concentration of the lithium salt is 0.5-1.5 mol/L. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • LiPF 6 lithium hexafluorophosphate
  • fluorine-containing lithium sulfonyl imide 0.5-1.5 mol/L. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • the fluorine-containing lithium sulfonimide includes lithium bisfluorosulfonimide, lithium fluoro(trifluoromethyl)sulfonimide, and lithium bis(trifluoromethyl)sulfonimide, At least one of lithium bis(pentafluoroethyl)sulfonimide and fluorine (lithium perfluorobutylsulfonimide) is preferably lithium bisfluorosulfonimide. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • the thickness of the negative electrode material layer is 30 ⁇ m-400 ⁇ m. As a result, the coating amount of the negative electrode active material can be increased, thereby increasing the energy density of the secondary battery.
  • a second aspect of the present application is to provide a battery module, which includes the secondary battery according to the first aspect of the present application.
  • a third aspect of the present application is to provide a battery pack, which includes the battery module according to the second aspect of the present application.
  • the fourth aspect of the present application is to provide an electric device, which includes the secondary battery according to the first aspect of the present application, the battery module according to the second aspect of the present application and the third aspect of the present application. at least one of the battery packs described above.
  • the fast charging capability of the secondary battery can be improved and the lithium deposition in the negative electrode can be suppressed.
  • FIG. 1 is a schematic diagram showing the pole piece tortuosity ⁇ .
  • FIG. 2 is a top SEM photograph of an example of the negative electrode material layer for explaining the calculation method of the pole piece tortuosity ⁇ .
  • FIG. 3 is a cross-sectional SEM photograph of an example of the negative electrode material layer for explaining the calculation method of the pole piece tortuosity ⁇ .
  • FIG. 4 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 4 .
  • Figure 6 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 8 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 7 .
  • FIG. 9 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 ⁇ 4 and 2 ⁇ 5.
  • the numerical range “a ⁇ b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0 ⁇ 5" means that all real numbers between "0 ⁇ 5" have been listed in this article, and "0 ⁇ 5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • the present application proposes a secondary battery, which includes: an electrode assembly and an electrolyte for infiltrating the electrode assembly; wherein the electrode assembly includes a negative electrode plate, a separator and a Positive electrode piece, the negative electrode piece includes a negative electrode current collector and a negative electrode material layer located on at least one surface of the negative electrode current collector.
  • the tortuosity of the negative electrode piece is ⁇ , then ⁇ satisfies the following formula I,
  • ⁇ is the porosity of the negative electrode material layer
  • ⁇ is the Bruggeman index of the negative electrode material
  • the inventor of the present application unexpectedly discovered after processing a large amount of experimental data that the secondary battery can obtain excellent fast charging characteristics by satisfying the above relationship between the tortuosity ⁇ of the negative electrode plate and the conductivity ⁇ of the electrolyte. .
  • the inventor of the present application speculates that there are two factors that restrict the fast charging capability of secondary batteries: 1) the transmission dynamics of lithium ions in the negative electrode; 2) the liquid phase diffusion ability of lithium ions in the electrolyte. If the performance of the two does not match, for example, the liquid phase transmission of lithium ions is relatively fast, but the kinetic properties of the anode material are poor, the lithium ions that migrate to the surface of the anode cannot diffuse into the inside of the anode in time, resulting in the lithium ions being reduced directly on the anode surface.
  • the tortuosity ⁇ of the pole piece represents the ratio of the migration path ⁇ L of lithium ions in the pole piece to the thickness ⁇ x of the pole piece.
  • the tortuosity ⁇ is closely related to the porosity ⁇ of the pole piece.
  • 0.5( ⁇ ) - ⁇ can be used to estimate the tortuosity ⁇ .
  • the Bruggeman index ⁇ can be calculated from the SEM photo of the negative electrode material layer using Wolfram Mathmatica software. Hereinafter, the calculation method of the Bruggeman index ⁇ will be explained with reference to FIGS. 2 and 3 .
  • Figure 2 is an example of a SEM photo of the top surface of the negative electrode material layer.
  • Figure 3 is an example of a cross-sectional SEM photograph of the negative electrode material layer.
  • the tortuosity ⁇ of the negative electrode piece and the conductivity ⁇ of the electrolyte can further satisfy: (2 ⁇ ) 0.5 +6 ⁇ ⁇ ⁇ (2 ⁇ ) 0.5 +8.
  • the dynamic properties of the negative electrode material and the electrolyte can be further matched to obtain better fast charging performance.
  • the ⁇ satisfies: 2.3 ⁇ 7.
  • the ⁇ ranges from 8 mS/cm to 14 mS/cm.
  • the conductivity ⁇ of the electrolyte is within the above range, the kinetic properties of the electrolyte can be improved, thereby further improving the fast charging characteristics of the secondary battery.
  • the porosity ⁇ of the negative electrode material layer is 25% to 45%.
  • the dynamic properties of the negative electrode material can be improved, thereby further improving the fast charging characteristics of the secondary battery.
  • the negative electrode material of the negative electrode sheet is graphite, and the ⁇ is 1.5 to 2.2.
  • the tortuosity of the negative electrode piece can be estimated more accurately.
  • the negative electrode material is not limited to graphite, and can also be other commonly used negative electrode materials.
  • the Bruggeman index ⁇ is also applicable to anode materials other than graphite.
  • the electrolyte includes cyclic ester, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, methyl acetate, methyl formate, ethyl formate, methyl propionate , propyl formate, ethyl propionate, and at least one of propyl acetate, and the cyclic ester includes at least one of ethylene carbonate and propylene carbonate. This makes it possible to easily adjust the conductivity of the electrolyte solution.
  • the lithium salt of the electrolyte contains at least one of lithium hexafluorophosphate (LiPF 6 ) and fluorine-containing lithium sulfonyl imide, and the concentration of the lithium salt is 0.5-1.5 mol/L. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • LiPF 6 lithium hexafluorophosphate
  • fluorine-containing lithium sulfonyl imide 0.5-1.5 mol/L. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • the fluorine-containing lithium sulfonimide includes lithium bisfluorosulfonimide, lithium fluoro(trifluoromethyl)sulfonimide, and lithium bis(trifluoromethyl)sulfonimide, At least one of lithium bis(pentafluoroethyl)sulfonimide and fluorine (lithium perfluorobutylsulfonimide) is preferably lithium bisfluorosulfonimide. This can further increase the conductivity of the electrolyte and suppress lithium deposition in the negative electrode.
  • the coating thickness of the negative electrode material layer is 30 ⁇ m-400 ⁇ m. As a result, the coating amount of the negative electrode active material can be increased, thereby increasing the energy density of the secondary battery.
  • a secondary battery is provided.
  • a secondary battery typically includes a negative electrode plate, a positive electrode plate, an electrolyte and a separator.
  • active ions are inserted and detached back and forth between the positive and negative electrodes.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes the positive electrode active material of the first aspect of the present application.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (such as LiCoO2), lithium nickel oxide (such as LiNiO2), lithium manganese oxide (such as LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium Manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi1/3Co1/3Mn1/3O2 (can also be abbreviated to NCM333), LiNi0.5Co0.2Mn0.3O2 (can also be abbreviated to NCM523), LiNi0 .5Co0.25Mn0.25O2 (can also be abbreviated to NCM211), LiNi0.6Co0.2Mn0.2O2 (can also be abbreviated to NCM622), LiNi0.8Co0.1Mn0.1O2 (can also be abbreviated to NCM811), lithium nickel cobalt aluminum oxide (such as LiNi0.85Co0.15Al0.05O2) and at least one of
  • lithium-containing phosphates with an olivine structure may include but are not limited to lithium iron phosphate (such as LiFePO4 (also referred to as LFP) ), at least one of composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO4), composite materials of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO4 (also referred to as LFP)
  • LiMnPO4 lithium manganese phosphate
  • composite materials of lithium manganese phosphate and carbon such as LiMnPO4
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, where the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative electrode film layer optionally further includes a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polysodium acrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • any well-known porous structure isolation membrane with electrochemical stability and mechanical stability can be selected according to actual needs.
  • it can include glass fiber, non-woven fabric, polyethylene. , single-layer or multi-layer films of one or more of polypropylene and polyvinylidene fluoride.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the type of electrolyte in this application can be selected according to needs.
  • the electrolyte can be liquid, gel, or completely solid.
  • the electrolyte is an electrolyte solution.
  • the electrolyte solution includes electrolyte salts, solvents and additives.
  • the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte includes additives, and the additives include fluorinated ethylene carbonate and/or vinylene carbonate.
  • additives include fluorinated ethylene carbonate and/or vinylene carbonate.
  • other additives may also be included, such as: negative electrode film-forming additives, positive electrode film-forming additives, Additives that can improve certain properties of the battery may also be included, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 4 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 6 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Figure 9 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • the device is usually required to be thin and light, and a secondary battery can be used as a power source.
  • the non-aqueous organic solvent includes 25.5 parts of ethylene carbonate and 59.5 parts of ethyl methyl carbonate. After mixing evenly, Slowly add 15 parts of lithium hexafluorophosphate (LiPF6) to the non-aqueous organic solvent. After the lithium salt is completely dissolved, the target electrolyte is obtained, which is the electrolyte. Test the room temperature conductivity of the target electrolyte.
  • LiPF6 lithium hexafluorophosphate
  • the electrolyte room temperature conductivity test is conducted in accordance with HG-T 4067-2015.
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , conductive agent Super P, and binder polyvinylidene fluoride (PVDF) were prepared in N-methylpyrrolidone (NMP) to prepare a positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the solid content in the positive electrode slurry is 50wt%, and the mass ratio of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , Super P, and PVDF in the solid content is 95:2:3.
  • porosity of different negative electrode material (graphite) layers can be adjusted by controlling the pressure of the cold pressing roller to control the compaction density of the pole piece.
  • PE polyethylene film
  • the inner ring area is fully filled with golden yellow on the surface of the negative electrode. Wipe it with dust-free paper. There is no gray metal lithium powder on the paper.
  • Slight lithium precipitation The inner ring area is full of dark yellow on the surface of the negative electrode. Wipe it with dust-free paper. There is gray metallic lithium powder on the paper.
  • Gray spots The inner ring area is full of gray on the surface of the negative electrode, with no golden color passing through.
  • Severe lithium precipitation The inner ring area is fully charged and the surface of the negative electrode is all gray, with no golden color passing through.
  • the preferred order of lithium precipitation in the negative electrode is no lithium precipitation>grey spots>slight lithium precipitation>severe lithium precipitation.
  • Example 2 to 8 and Comparative Examples 1 to 2 in addition to changing the types and contents of each raw material of the electrolyte as shown in Table 1, the particle size of the negative electrode material and the size of the negative electrode piece were changed as shown in Table 2. Except for parameters such as compaction density, the same preparation method as in Example 1 was used to obtain each secondary battery.
  • Examples 1 to 5 that satisfy (2 ⁇ ) 0.5 + 6 ⁇ ⁇ ⁇ (2 ⁇ ) 0.5 + 8 can obtain better fast charging performance and can go further. Inhibit lithium evolution from the negative electrode.

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Abstract

提供一种二次电池（5）、电池模块（4）、电池包（1）及用电装置。二次电池（5）包括：电极组件（52）以及用于浸润电极组件（52）的电解液；其中，电极组件（52）包括负极极片、隔离膜和正极极片，负极极片包括负极集流体以及位于负极集流体至少一个表面的负极材料层，设负极极片的迂曲度为τ，则τ满足式I，τ＝0.5(ε) - α 式I 其中，ε为负极材料层的孔隙率，α为负极材料的Bruggeman指数，τ与电解液的电导率σ满足式II， (2τ) 0.5+6≤σ≤(2τ) 0.5+10 式II。如此二次电池（5）具有优异的快充性能。

Description

二次电池、电池模块、电池包及用电装置 技术领域
本申请涉及电池领域，尤其涉及一种二次电池、电池模块、电池包和用电装置。
背景技术
二次电池具有工作性能可靠，以及无污染、无记忆效应等优点，因而被广泛应用。例如，随着环境保护问题日益受到重视，新能源汽车日益普及，动力型二次电池的需求将呈现爆发式增长。然而，随着二次电池的应用范围越来越广泛，对二次电池的性能也提出了严峻挑战。
随着生活节奏的变快，人们除了对二次电池循环寿命有强烈需求外，快充性能也是人们必须要考虑的问题。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种二次电池、电池模块、电池包和用电装置，该二次电池具有优异的快充性能。
为了实现上述目的，本申请第一方面在于提供一种二次电池，其中，包括：电极组件以及用于浸润所述电极组件的电解液；其中，所述电极组件包括负极极片、隔离膜和正极极片，所述负极极片包括负极集流体以及位于所述负极集流体至少一个表面的负极材料层，设所述负极极片的迂曲度为τ，则τ满足下述式I，
τ＝0.5(ε) -α     式I
其中，ε为所述负极材料层的孔隙率，α为负极材料的Bruggeman指数，
所述τ与电解液的电导率σ满足下述式II，
(2τ) 0.5+6≤σ≤(2τ) 0.5+10     式II。
通过负极极片的迂曲度τ与电解液的电导率σ满足上述关系，能够使二次电池获得优异的快充特性并抑制负极析锂。
在一些实施方式中，所述τ满足：2.3≤τ≤7。通过使迂曲度τ在上述范围内，从而提高负极材料的动力学性能，进一步提高二次电池的快充特性。
在一些实施方式中，所述σ的范围为8mS/cm至14mS/cm。通过电解液的电导率σ在上述范围内，能够提高电解液的动力学性能，从而进一步提高二次电池的快充特性。
在一些实施方式中，所述负极材料层的孔隙率ε为25％至45％。通过负极材料层的孔隙率在该范围内，能够提高负极材料的动力学性能，从而能够进一步提高二次电池的快充特性。
在一些实施方式中，所述负极材料为石墨，所述α为1.5～2.2。由此，能够更准确地估算负极极片的迂曲度。
在一些实施方式中，所述电解液包含环状酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、乙酸乙酯、乙酸甲酯、甲酸甲酯、甲酸乙酯、丙酸甲酯、甲酸丙酯、丙酸乙酯，乙酸丙酯中至少的一种，所述环状酯包含碳酸乙烯酯、碳酸丙烯酯中的至少一种。由此，能够容易调节电解液的电导率。
在一些实施方式中，所述电解液的锂盐包含六氟磷酸锂(LiPF 6)、含氟磺酰亚胺锂中的至少一种，所述锂盐的浓度为0.5-1.5mol/L。由此，能够进一步增加电解液的电导率，并抑制负极析锂。
在一些实施方式中，所述含氟磺酰亚胺锂包括双氟磺酰亚胺锂、氟(三氟甲基)磺酰亚胺锂、双(三氟甲基)磺酰亚胺锂，双(五氟乙基)磺酰亚胺锂、氟(全氟丁基磺酰亚胺锂)中的至少一种，优选为双氟磺酰亚胺锂。由此，能够进一步增加电解液的电导率，并抑制负极析锂。
在一些实施方式中，在所述负极极片中，所述负极材料层的厚度为30μm-400μm。由此，能够提高负极活性材料的涂覆量，进而提高二次电池的能量密度。
本申请第二方面在于提供一种电池模块，该电池模块包括根据本申请第一方面所述的二次电池。
本申请第三方面在于提供一种电池包，该电池包包括根据本申请第二方面所述的电池模块。
本申请第四方面在于提供一种用电装置，该用电装置包括根据本申请第一方面所述的二次电池、根据本申请第二方面所述的电池模块和根据本申请第三方面所述的电池包中的至少一种。
根据本申请，能够提高二次电池的快充能力并抑制负极析锂。
附图说明
图1是表示极片迂曲度τ的示意图。
图2是用于说明极片迂曲度τ的计算方法的负极材料层的一个示例的顶面SEM照片。
图3是用于说明极片迂曲度τ的计算方法的负极材料层的一个示例的截面SEM照片。
图4是本申请一实施方式的二次电池的示意图。
图5是图4所示的本申请一实施方式的二次电池的分解图。
图6是本申请一实施方式的电池模块的示意图。
图7是本申请一实施方式的电池包的示意图。
图8是图7所示的本申请一实施方式的电池包的分解图。
图9是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的正极活性材料及其制造方法、正极极片、二次电池、电池模块、电池包和电学装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围 是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60～120和80～110的范围，理解为60～110和80～120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1～3、1～4、1～5、2～3、2～4和2～5。在本申请中，除非有其他说明，数值范围“a～b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0～5”表示本文中已经全部列出了“0～5”之间的全部实数，“0～5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
本申请的一个实施方式中，本申请提出了一种二次电池，其中，包括：电极组件以及用于浸润所述电极组件的电解液；其中，所述电极组件包括负极极片、隔离膜和正极极片，所述负极极片包括负极集流体以及位于所述负极集流体至少一个表面的负极材料层，设所述负极极片的迂曲度为τ，则τ满足下述式I，
τ＝0.5(ε) -α      式I
其中，ε为所述负极材料层的孔隙率，α为负极材料的Bruggeman指数，
所述τ与电解液的电导率σ满足下述式II，
(2τ) 0.5+6≤σ≤(2τ) 0.5+10       式II。
虽然机理尚不明确，但本申请发明人处理大量实验数据后意外地发现：通过负极极片的迂曲度τ与电解液的电导率σ满足上述关系，能够使二次电池获得优异的快充特性。
本申请发明人推测：制约二次电池快充能力的因素有两个：1)锂离子在负极中的传输动力学性能；2)锂离子在电解液中的液相扩散能力。如果两者性能不匹配，比如锂离子液相传输比较快，但是负极材料的动力学性能较差，则迁移到负极表面的锂离子不能及时扩散到负极内部会导致锂离子直接在阳极表面被还原成金属锂，即“阳极析锂”，导致安全风险；如果负极材料的动力学性能较好，但是锂离子在电解液中的液相扩散能力较弱，则会导致从正极脱出的锂离子不能及时到达负极，导致二次电池充电容量降低。因此只有负极材料与电解液的动力学性能匹配时，才能得到良好的快充性能。
此处，如图1所示，极片的迂曲度τ表示极片中锂离子的迁移路径ΔL与极片厚度Δx的比值。迂曲度τ与极片的孔隙率ε密切相关，对于不同的负极材料，可以采用0.5(ε) -α来估算迂曲度τ。
Bruggeman指数α可以利用Wolfram Mathmatica软件对负极材料层的SEM照片进行计算而得到。以下，参照图2、3，说明Bruggeman指数α的计算方法。
首先，对于制作完成的负极极片获取负极材料层的顶面与截面的SEM照片。图2为负极材料层的顶面SEM照片的一个例子。图3为负极材料层的截面SEM照片的一个例子。
其次，利用Wolfram Mathmatica软件，在负极材料层的顶面与截面的SEM照片中，手动标出50～90个活性颗粒的长轴和短轴，并拟合出各活性颗粒的外形轮廓。
最后，利用Wolfram Mathmatica软件，根据上述获得的标出活性颗粒外形轮廓的负极材料层的顶面与截面的SEM照片，计算负极材料层平面方向的Bruggeman指数α x、α y以及法线方向(截面方向)的 Bruggeman指数α z。上述式(ε) -α中的α即为此处法线方向(截面方向)的Bruggeman指数α z。
另外，对于上述制得的极片进行孔隙率测试，极片孔隙率的测试方法参照GB/T 24586-2009进行。
在一些实施方式中，负极极片的迂曲度τ与电解液的电导率σ可以进一步满足：(2τ) 0.5+6≤σ≤(2τ) 0.5+8。由此，能够进一步将负极材料与电解液的动力学性能匹配，得到更好的快充性能。
在一些实施方式中，所述τ满足：2.3≤τ≤7。通过使迂曲度τ在上述范围内，从而提高负极材料的动力学性能，进一步提高二次电池的快充特性。
在一些实施方式中，所述σ的范围为8mS/cm至14mS/cm。通过电解液的电导率σ在上述范围内，能够提高电解液的动力学性能，从而进一步提高二次电池的快充特性。
在一些实施方式中，所述负极材料层的孔隙率ε为25％至45％。通过负极材料层的孔隙率在该范围内，能够提高负极材料的动力学性能，从而能够进一步提高二次电池的快充特性。
在一些实施方式中，所述负极极片的负极材料为石墨，所述α为1.5～2.2。由此，能够更准确地估算负极极片的迂曲度。需要说明的是，负极材料不限于石墨，也可以是其他常用的负极材料。Bruggeman指数α对石墨以外的负极材料同样适用。
在一些实施方式中，所述电解液包含环状酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、乙酸乙酯、乙酸甲酯、甲酸甲酯、甲酸乙酯、丙酸甲酯、甲酸丙酯、丙酸乙酯，乙酸丙酯中至少的一种，所述环状酯包含碳酸乙烯酯、碳酸丙烯酯中的至少一种。由此，能够容易调节电解液的电导率。
在一些实施方式中，所述电解液的锂盐包含六氟磷酸锂(LiPF 6)、含氟磺酰亚胺锂中的至少一种，所述锂盐的浓度为0.5-1.5mol/L。由此，能够进一步增加电解液的电导率，并抑制负极析锂。
在一些实施方式中，所述含氟磺酰亚胺锂包括双氟磺酰亚胺锂、氟(三氟甲基)磺酰亚胺锂、双(三氟甲基)磺酰亚胺锂，双(五氟乙基)磺酰亚胺锂、氟(全氟丁基磺酰亚胺锂)中的至少一种，优选 为双氟磺酰亚胺锂。由此，能够进一步增加电解液的电导率，并抑制负极析锂。
在一些实施方式中，在所述负极极片中，负极材料层的涂布厚度为30μm-400μm。由此，能够提高负极活性材料的涂覆量，进而提高二次电池的能量密度。
另外，以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
[二次电池]
本申请的一个实施方式中，提供一种二次电池。
通常情况下，二次电池包括负极极片、正极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括本申请第一方面的正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电 池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)、锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面， 负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[隔离膜]
作为上述的隔离膜，本申请并没有特别的限制，可以根据实际需 求选用任意公知的具有电化学稳定性和力学稳定性的多孔结构隔离膜，例如可以是包含玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的一种或几种的单层或多层薄膜。
[电解液]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐、溶剂和添加剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，所述电解液包括添加剂，所述添加剂包括氟代碳酸乙烯酯和/或碳酸亚乙烯酯，此外，还可以包括其它添加剂，例如：负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图4是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图5，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
电池模块
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图6是作为一个示例的电池模块4。参照图6，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
电池包
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图7和图8是作为一个示例的电池包1。参照图7和图8，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
用电装置
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能***等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图9是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
<实施例1>
①制备方法
(1)电解液的制备
在充满氩气的手套箱中(水含量＜10ppm，氧气含量＜1ppm)，设质量总量为100份，非水有机溶剂包括25.5份碳酸乙烯酯、59.5份碳酸甲乙酯，混合均匀后，向非水有机溶剂中缓慢加入15份的六氟磷酸锂(LiPF6)，待锂盐完全溶解后，得到目标电解液，即为所述电解液。测试目标电解液的室温电导率。
电解液室温电导率测试参照HG-T 4067-2015进行测试。
(2)正极片的制备：
将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、导电剂Super P、粘结剂聚偏 二氟乙烯(PVDF)在N-甲基吡咯烷酮(NMP)中制成正极浆料。正极浆料中固体含量为50wt％，固体成分中LiNi 0.5Co 0.2Mn 0.3O 2、Super P、PVDF的质量比为95:2:3。将正极浆料涂布在集流体铝箔上并在85℃下烘干后进行冷压，然后进行切边、裁片、分条后，在85℃的真空条件下烘干4h，制成正极片。
(3)负极材料-石墨A的制备：准备平均粒径Dv50为15μm的石墨作为负极材料。该石墨的Bruggeman指数α为1.9。本领域技术人员可以通过调节石墨的平均粒径参数，实现对石墨的Bruggeman指数α的调变。
需要说明的是，石墨B和石墨C本领域技术人员同样可以通过调节石墨的粒径得到。
(4)负极片的制备：
将作为负极活性材料的上述石墨与导电剂Super P、增稠剂CMC、粘接剂丁苯橡胶(SBR)在去离子水中混合均匀，制成负极浆料。负极浆料中固体含量为30wt％，固体成分中石墨、Super P、CMC及粘接剂丁苯橡胶(SBR)的质量比为94:3:3将负极浆料涂布在集流体铜箔上并在85℃下烘干，然后进行冷压、切边、裁片、分条后，在120℃真空条件下烘干12h，制成负极片。此处，冷压时冷压辊的压力为38T，得到压实密度为1.24g/cm 3，孔隙率为45％的极片。
需要说明的是，不同负极材料(石墨)层的孔隙率可以通过控制冷压辊的压力来控制极片的压实密度而调整。
(5)锂离子电池的制备：
以16μm的聚乙烯薄膜(PE)作为隔离膜。将制得的正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正负极片中间起到隔离正负极的作用，卷绕得到裸电芯，焊接极耳，将裸电芯置于外包装中，将上述制备的电解液注入到干燥后的电芯中，封装、静置、化成、整形、容量测试等，完成锂离子电池的制备(软包锂离子电池的厚度4.0mm、宽度60mm、长度140mm)。
② 性能评价
(i)电解液的室温电导率
对于上述(1)中制得的电解液进行电导率测试，电解液室温电导率 测试参照HG-T 4067-2015进行测试。
(ii)极片的孔隙率测试
对于上述(3)中制得的极片进行孔隙率测试，极片孔隙率的测试方法参照GB/T 24586-2009进行。
(iii)快充性能测试
对于上述(4)中制得的电池，25℃下将锂离子电池以1C恒流充电至4.25V，然后以4.25V恒压充电至电流为0.05C，然后用1C恒流放电至2.8V，记录电池的放电容量D0，随后4C恒流充电到4.25V，然后以4.25V恒压充电至电流为0.05C，然后用1C恒流放电至2.8V，记录放电容量D1，放电容量保持率为：D1/D0。
(iv)负极析锂情况
将化成后的电池在25℃下，以2C恒流充电至4.25V，然后以4.25V恒压充电至电流小于0.05C，然后再以1C放电到2.8V，循环10圈后，再以2C恒流充电至4.25V，然后以4.25V恒压充电至电流小于0.05C得到满充电池。
将循环了10圈以后的电池拆解，观察负极析锂情况。
观察后的评价基准如下。
不析锂：内圈区域满充负极表面金黄色，用无尘纸擦拭，纸上无灰色金属锂粉。
轻微析锂：内圈区域满充负极表面暗黄色，用无尘纸擦拭，纸上有灰色金属锂粉。
灰斑：内圈区域满充负极表面局部灰色，无金黄色透过。
严重析锂：内圈区域满充负极表面全部是灰色，无金黄色透过。
本申请中，负极析锂的优选次序为不析锂>灰斑>轻微析锂>严重析锂。
<实施例2>至<实施例8>、<对比例1>至<对比例2>
在实施例2至8、以及对比例1至2中，除了如表1所示变更电解液各原料的种类和含量外、以及，如表2所示变更负极材料的粒径、负极极片的压实密度等参数外，采用与实施例1相同的制备方法，由此得到各二次电池。
[表1]
Figure PCTCN2022096609-appb-000001
Figure PCTCN2022096609-appb-000002
由表2的测试结果可以得知，对应于不同的负极材料，满足(2τ) 0.5+6≤σ≤(2τ) 0.5+10的实施例1至8与对比例1、2相比，其快充性能得到显著改善，并且负极析锂状况也有明显改善。由此可知，负极与电解液动力学性能相匹配时，能够得到良好的快充性能并避免负极析锂。对比例1中，电解液的电导率太低，锂离子在液相中迁移太慢，从正极脱出的锂离子不能及时嵌入负极，而是聚集在正极，导致正极电极电位快速抬升，达到截止电位，因此放电容量保持率较低，此外，外电路中电子转移到负极，负极电位降低，锂离子迁移到负极时可能就已经达到了析锂电位，因此出现析锂。而对比例2中，电解液电导率过高，充电时，从正极脱出的锂离子快速达到负极，但是负极动力学较差，使得聚集在负极界面的锂离子不能快速的嵌入负极，随着负极电位的降低，界面上的锂离子被还原成金属锂，成为“死锂”，因此快充性能也比较差。
另外，从实施例1至5和实施例6的对比可知，满足(2τ) 0.5+6≤σ≤(2τ) 0.5+8的实施例1至5能够获得更优异的快充性能并能够更进一步抑制负极析锂。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (12)

  1. 一种二次电池，其中，
    包括：电极组件以及用于浸润所述电极组件的电解液；其中，
    所述电极组件包括负极极片、隔离膜和正极极片，所述负极极片包括负极集流体以及位于所述负极集流体至少一个表面的负极材料层；
    设所述负极极片的迂曲度为τ，则τ满足下述式I，
    τ＝0.5(ε) -α  式I
    其中，ε为所述负极材料层的孔隙率，α为所述负极材料的Bruggeman指数，
    所述τ与所述电解液的电导率σ满足下述式II，
    (2τ) 0.5+6≤σ≤(2τ) 0.5+10  式II。
  2. 根据权利要求1所述的二次电池，其中，
    所述τ满足：2.3≤τ≤7。
  3. 根据权利要求1或2所述的二次电池，其中，
    所述σ的范围为8mS/cm至14mS/cm。
  4. 根据权利要求1至3中任一项所述的二次电池，其中，
    所述负极材料层的孔隙率ε为25％至45％。
  5. 根据权利要求1至4中任一项所述的二次电池，其中，
    所述负极材料为石墨，所述α为1.5～2.2。
  6. 根据权利要求1至5中任一项所述的二次电池，其中，
    所述电解液包含碳酸乙烯酯、碳酸丙烯酯中的至少一种环状酯，以及碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、乙酸乙酯、乙酸甲酯、甲酸甲酯、甲酸乙酯、丙酸甲酯、甲酸丙酯、丙酸乙酯，乙酸丙酯中至少的一种。
  7. 根据权利要求1至6中任一项所述的二次电池，其中，
    所述电解液的锂盐包含六氟磷酸锂、含氟磺酰亚胺锂中的至少一种，所述锂盐的浓度为0.5-1.5mol/L。
  8. 根据权利要求7所述的二次电池，其中，
    所述含氟磺酰亚胺锂包括双氟磺酰亚胺锂、氟(三氟甲基)磺酰亚胺锂、双(三氟甲基)磺酰亚胺锂，双(五氟乙基)磺酰亚胺锂、氟(全氟丁基磺酰亚胺锂)中的至少一种，优选为双氟磺酰亚胺锂。
  9. 根据权利要求1至8中任一项所述的二次电池，其中，
    在所述负极极片中，所述负极材料层的厚度为30μm-400μm。
  10. 一种电池模块，其中，
    包括权利要求1至9中任一项所述的二次电池。
  11. 一种电池包，其中，
    包括选自权利要求1至9中任一项所述的二次电池或权利要求10所述的电池模块中的至少一种。
  12. 一种用电装置，其中，
    包括选自权利要求1至9中任一项所述的二次电池、权利要求10所述的电池模块或权利要求11所述的电池包中的至少一种。
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