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WO2025077847A1 - Positive electrode sheet and battery comprising same - Google Patents

Positive electrode sheet and battery comprising same Download PDF

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Publication number
WO2025077847A1
WO2025077847A1 PCT/CN2024/124238 CN2024124238W WO2025077847A1 WO 2025077847 A1 WO2025077847 A1 WO 2025077847A1 CN 2024124238 W CN2024124238 W CN 2024124238W WO 2025077847 A1 WO2025077847 A1 WO 2025077847A1
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WIPO (PCT)
Prior art keywords
positive electrode
lithium
rich manganese
electrode sheet
based material
Prior art date
Application number
PCT/CN2024/124238
Other languages
French (fr)
Chinese (zh)
Inventor
张周昱
陈博
陈莎
陈瑶
李俊义
Original Assignee
珠海冠宇动力电池有限公司
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Publication of WO2025077847A1 publication Critical patent/WO2025077847A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure belongs to the technical field of batteries, and in particular relates to a positive electrode sheet and a battery including the positive electrode sheet.
  • the industry's requirements for the energy density and fast charging performance of its power batteries are also increasing.
  • the battery positive electrode has an important impact on the battery's cycle life and energy density.
  • the existing commercial positive electrode is difficult to meet the future industry's higher performance requirements for power batteries. Therefore, it is very important to invent a battery with high energy density, high cycle stability and high rate performance.
  • lithium-rich manganese-based materials have high theoretical gram capacity (>250mAh/g) and charging voltage ( ⁇ 4.5V), making them candidate materials for high energy density batteries.
  • charging voltage ⁇ 4.5V
  • the purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and provide a positive electrode sheet and a battery including the positive electrode sheet.
  • the positive electrode sheet disclosed in the present invention has good conductivity, so that the positive electrode sheet has high specific capacity and high cycle stability; the battery including the positive electrode sheet disclosed in the present invention has high energy density, high cycle stability and high rate performance.
  • the battery's cycle stability and rate performance can be improved by improving the conductivity of the positive electrode.
  • the positive electrode in order to improve the conductivity of the positive electrode, the positive electrode can be changed
  • the structure of the positive electrode has a high cycle stability. After a lot of in-depth research, a specific structure that can improve the conductivity of the positive electrode has been selected.
  • the first aspect of the present disclosure provides a positive electrode sheet, which includes a positive electrode collector and a positive electrode paste located on one side or both sides of the positive electrode collector, the positive electrode paste includes a lithium-rich manganese-based material and a conductive material, the conductive material includes carbon nanotubes, and the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is (233 ⁇ 2.6 ⁇ 10 4 ):1.
  • a second aspect of the present disclosure provides a battery, comprising the positive electrode sheet described in the first aspect of the present disclosure.
  • the present disclosure has at least the following advantages compared with the prior art:
  • the positive electrode sheet disclosed in the present invention can have a lower electrode resistivity and a higher conductivity with a lower amount of conductive agent through the synergistic combination of lithium-rich manganese-based materials and carbon nanotubes, thereby improving the gram capacity of the positive electrode sheet, increasing the energy density of the battery, and enhancing the rate performance and cycle stability of the battery.
  • FIG1 is a schematic diagram showing the structure of the positive electrode sheet of the present invention (wherein 1 is the positive electrode current collector, 2 is the positive electrode paste, 21 is the lithium-rich manganese-based material, 22 is the conductive material, 221 is the carbon nanotube, 222 is the conductive agent, and 3 is the separator).
  • FIG. 2 is a scanning electron microscope (SEM) image of the positive electrode sheet of Example 1 of the present disclosure.
  • a first aspect of the present disclosure provides a positive electrode sheet, comprising a positive electrode collector and a positive electrode paste located on one side or both sides of the positive electrode collector, wherein the positive electrode paste comprises a lithium-rich manganese-based material and a conductive material, wherein the conductive material comprises carbon nanotubes, and the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is (233-2.6 ⁇ 10 4 ):1.
  • the positive electrode sheet includes a positive electrode current collector 1 and a positive electrode paste 2 located on one side or both sides of the positive electrode current collector 1, wherein the positive electrode paste 2 includes a lithium-rich manganese-based material 21 and a conductive material 22, wherein the conductive material 22 includes a carbon nanotube 221 and a conductive agent 222.
  • the carbon nanotube has a strong conductivity, and the addition of the carbon nanotube to the conductive material can improve the problem of poor conductivity of the lithium-rich manganese-based material, thereby compensating for the current density difference between the surface layer (the side of the paste away from the positive electrode current collector) and the bottom layer (the side of the paste close to the positive electrode current collector) of the positive electrode sheet, improving the resistivity of the paste, and at the same time, based on the large aspect ratio of the carbon nanotube, a conductive network can be constructed between the lithium-rich manganese-based materials, thereby improving the uniformity of the overall current density of the positive electrode sheet, reducing polarizability, and increasing the depth of lithium deintercalation of the lithium-rich manganese-based material, thereby improving the performance of the specific capacity of the positive electrode sheet and improving the energy density of the battery.
  • the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotube may be (233-2.6 ⁇ 10 4 ):1 (for example, 233:1, 265:1, 3 ⁇ 10 3 :1, 3.5 ⁇ 10 3 :1, 4 ⁇ 10 3 :1, 4.5 ⁇ 10 3 :1, 5 ⁇ 10 3 :1, 5.5 ⁇ 10 3 :1, 6 ⁇ 10 3 :1, 6.5 ⁇ 10 3 :1, 7 ⁇ 10 3 :1, 7.5 ⁇ 10 3 :1, 8 ⁇ 10 3 :1, 9 ⁇ 10 3 :1, 1 ⁇ 10 4 :1, 2 ⁇ 10 4 :1, 2.5 ⁇ 10 4 :1 , 2.6 ⁇ 10 4 :1).
  • the carbon nanotubes can form a three-dimensional conductive network between the lithium-rich manganese-based materials, thereby improving the conductivity of the positive electrode sheet, and improving the cycle stability and rate performance of the battery.
  • the surface of the lithium-rich manganese-based material is uniformly coated with carbon nanotubes and other conductive agents, and the conductive network formed by the carbon nanotubes between the lithium-rich manganese-based materials can improve the conductivity of the positive electrode sheet, thereby improving the cycle stability and rate performance of the battery.
  • the carbon nanotubes are not easy to contact each other between the lithium-rich manganese-based materials, and it is not easy to form a continuous conductive path, thereby deteriorating the conductivity of the positive electrode sheet;
  • the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is higher than 2.6 ⁇ 10 4 :1, due to the poor dispersion effect of the carbon nanotubes, uneven dispersion is likely to occur, and a uniform conductive network cannot be formed between the lithium-rich manganese-based materials, thereby making the conductivity of the positive electrode sheet weaker.
  • the uniformity of the current density of the positive electrode sheet can be improved, the specific capacity of the positive electrode sheet can be improved, thereby increasing the energy density of the battery, and the conductivity of the positive electrode sheet can be improved, thereby improving the cycle stability and rate performance of the battery.
  • the positive electrode sheet By designing the positive electrode sheet to have the above-mentioned specific structure, the positive electrode sheet can achieve higher specific capacity, higher cycle stability and higher rate performance than the prior art. In order to further improve the effect, one or more of the technical features can be further optimized.
  • the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (2.6 ⁇ 10 3 to 2.4 ⁇ 10 4 ): 1. Limiting the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube within the above-mentioned specific range can further improve the conductivity of the conductive network formed by the carbon nanotubes, thereby further improving the cycle stability and rate performance of the battery.
  • the diameter of the carbon nanotube is 0.5 nm to 30 nm (eg, 0.5 nm, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm).
  • the length of the carbon nanotubes is less than 30 ⁇ m.
  • the diameter of the carbon nanotube is 0.5 nm to 30 nm and the length of the carbon nanotube is less than 30 ⁇ m.
  • the diameter and length of the carbon nanotubes can be obtained by observing a dispersion containing a sample under a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the carbon nanotubes include single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
  • the carbon nanotubes are single-walled carbon nanotubes.
  • Single-walled carbon nanotubes have a simpler structure, more stable chemical properties, and a smaller aspect ratio than multi-walled carbon nanotubes. Therefore, when single-walled carbon nanotubes are used, a relatively small amount of single-walled carbon nanotubes can be used to form a better three-dimensional conductive network between the lithium-rich manganese-based materials, thereby improving the conductivity of the positive electrode sheet and improving the cycle stability and rate performance of the battery.
  • the diameter of the single-walled carbon nanotube is 0.5 nm-3 nm (e.g., 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 2.9 nm, 3 nm), and/or the length of the single-walled carbon nanotube is 600 nm-8400 nm (e.g., 600 nm, 1000 nm, 1500 nm, 1800 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, 5500 nm, 6000 nm, 8000 nm, 9000 nm, 10000 nm, 15000 nm, 1800 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, 5500 nm, 6000 nm, 8 nm,
  • the diameter of the single-walled carbon nanotube is 0.5nm-3nm
  • the length of the single-walled carbon nanotube is 600nm-8400nm
  • the aspect ratio of the single-walled carbon nanotube is (200-16800): 1.
  • the diameter of the single-walled carbon nanotube is 0.5nm-3nm (for example, 0.5nm, 0.7nm, 1nm, 1.2nm, 1.5nm, 1.7nm, 2nm, 2.2nm, 2.5nm, 2.7nm, 3nm), and/or the length of the single-walled carbon nanotube is 3000nm-6000nm (for example, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, 5500nm, 6000nm), and/or the aspect ratio of the single-walled carbon nanotube is (1000-12000):1 (for example, 1000:1, 3000:1, 5000:1, 7000:1, 10000:1, 12000:1).
  • the conductive material further includes a conductive agent.
  • the weight ratio of the carbon nanotubes to the conductive agent is (0.002-1.5):1.
  • the weight ratio of carbon nanotubes to the weight of the conductive agent is lower than 0.002:1, too few carbon nanotubes will be unfavorable for building a three-dimensional conductive network; when the weight ratio of carbon nanotubes to the weight of the conductive agent is higher than 1.5:1, too many carbon nanotubes are prone to agglomeration, making them unevenly dispersed.
  • the weight ratio of carbon nanotubes to the weight of the conductive agent is within the above-mentioned specific range, a good conductive network can be formed while maintaining uniform dispersion, thereby improving the conductive performance of the electrode.
  • the weight ratio of the carbon nanotubes to the conductive agent is (0.002-0.14):1.
  • the conductive material further includes a conductive agent, which includes one or more of conductive carbon black (such as Ketjen black, acetylene black, KS-6, KS-15, S-O), carbon fiber and graphene (such as SEG-6).
  • a conductive agent which includes one or more of conductive carbon black (such as Ketjen black, acetylene black, KS-6, KS-15, S-O), carbon fiber and graphene (such as SEG-6).
  • the chemical formula of the lithium-rich manganese-based material is xLi 2 MnO 3 ⁇ (1-x)LiM z N y O 2 .
  • the elements comply with the principle that the algebraic sum of positive and negative valences of the elements in the compound is zero.
  • x can be a decimal, for example, x is 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.
  • y can be a decimal, for example, y is 0, 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.
  • y can be a decimal, for example, y is 0, 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.
  • M may include one or more of Ni, Co and Mn.
  • M is a plurality of elements
  • the sum of the atomic numbers of the plurality of elements is z.
  • M is Ni and Mn
  • the sum of the atomic number of Ni and the atomic number of Mn is z.
  • N may include transition metal elements, preferably N includes one or more of Al, Cr, Nb, Mg, Mo, Ta and V.
  • N is a plurality of elements
  • the sum of the atomic numbers of the plurality of elements is y.
  • the sum of the atomic number of Al and the atomic number of Nb is y.
  • the specific surface area of the lithium-rich manganese-based material is 1 m 2 /g to 4 m 2 /g (e.g., 1 m 2 /g, 1.2 m 2 /g, 1.5 m 2 /g, 2 m 2 /g, 2.5 m 2 /g, 3 m 2 /g, 3.2 m 2 /g, 4 m 2 /g).
  • the specific surface area of the lithium-rich manganese-based material is 1.5 m 2 /g to 3 m 2 /g.
  • the specific surface area of the lithium-rich manganese-based material is controlled within the above range, sufficient contact between the positive electrode active material and the electrolyte can be ensured to have good lithium insertion and extraction capabilities, while no serious side reactions will occur due to excessive contact area.
  • the tap density of the lithium-rich manganese-based material is 1 g/cm 3 to 3 g/cm 3 (eg, 1 g/cm 3 , 1.2 g/cm 3 , 1.5 g/cm 3 , 1.7 g/cm 3 , 2 g/cm 3 , 2.5 g/cm 3 , 3 g/cm 3 ).
  • the tap density of the lithium-rich manganese-based material is 1.2 g/cm 3 to 2 g/cm 3 .
  • the tap density of the lithium-rich manganese-based material is controlled within the above range, the internal space utilization of the positive electrode plate can be effectively improved, and sufficient contact between the active material and the conductive material can be ensured, thereby improving the conductive performance of the plate.
  • the lithium-rich manganese-based material includes a polycrystalline structure.
  • the “polycrystalline structure” means that each active material particle itself is formed by the aggregation of multiple primary particle crystals with smaller particle sizes.
  • the median particle size Dv50 of the lithium-rich manganese-based material is 7 ⁇ m to 13 ⁇ m (for example, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m, 10 ⁇ m, 10.5 ⁇ m, 11.5 ⁇ m, 12 ⁇ m, 12.5 ⁇ m, 13 ⁇ m).
  • the lithium-rich manganese-based material particles can be kept uniformly dispersed, the space utilization rate can be improved, and the lithium-rich manganese-based material particles can be uniformly contacted with the conductive material (including carbon nanotubes and other conductive agents) to form a uniform and good conductive network to improve the overall conductivity of the positive electrode.
  • the conductive material including carbon nanotubes and other conductive agents
  • the median particle size Dv50 of the lithium-rich manganese-based material is 8 ⁇ m to 12 ⁇ m.
  • the Dv10 of the lithium-rich manganese-based material is 1 ⁇ m to 7 ⁇ m (for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m).
  • the lithium-rich manganese-based material particles can be kept uniformly dispersed, the space utilization rate can be improved, and the conductive material (including carbon nanotubes and other conductive agents) can be uniformly contacted to form a uniform and good conductive network to improve the overall conductivity of the positive electrode.
  • the Dv10 of the lithium-rich manganese-based material is 3 ⁇ m to 6 ⁇ m.
  • the Dv90 of the lithium-rich manganese-based material is 13 ⁇ m to 23 ⁇ m (for example, By controlling the Dv90 of the material within the above range, the lithium-rich manganese-based material particles can be uniformly dispersed, the space utilization rate can be improved, and the lithium-rich manganese-based material particles can be uniformly contacted with the conductive material (including carbon nanotubes and other conductive agents) to form a uniform and good conductive network, so as to improve the overall conductive performance of the positive electrode.
  • the conductive material including carbon nanotubes and other conductive agents
  • the Dv90 of the lithium-rich manganese-based material is 15 ⁇ m to 20 ⁇ m.
  • the median particle sizes Dv50, Dv10 and Dv90 can be obtained by testing with a particle size analyzer.
  • DvN (such as Dv10, Dv50, Dv90) refers to the particle size corresponding to when the cumulative volume particle size distribution percentage of a sample reaches N%.
  • Dv10 the particle size at which the cumulative distribution of particles is 10%, that is, the volume content of particles less than or equal to this particle size accounts for 10% of all particles
  • Dv50 the particle size at which the cumulative distribution of particles is 10%, that is, the volume content of particles less than or equal to this particle size accounts for 50% of all particles
  • Dv90 the particle size at which the cumulative distribution of particles is 90%, that is, the volume content of particles less than or equal to this particle size accounts for 90% of all particles.
  • the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (233-2.6 ⁇ 10 4 ): 1, and the median particle size Dv50 of the lithium-rich manganese-based material is 7 ⁇ m-13 ⁇ m, the Dv10 of the lithium-rich manganese-based material is 1 ⁇ m-7 ⁇ m, and the Dv90 of the lithium-rich manganese-based material is 13 ⁇ m-23 ⁇ m.
  • the lithium-rich manganese-based material particles can be uniformly dispersed, the space utilization rate can be improved, the lithium-rich manganese-based material and the carbon nanotubes can be better matched, a uniform and good conductive network can be formed, and the conductive performance of the conductive network can be further improved.
  • the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (2.8 ⁇ 10 3 to 2.4 ⁇ 10 4 ): 1, and the median particle size Dv50 of the lithium-rich manganese-based material is 8 ⁇ m to 12 ⁇ m, the Dv10 of the lithium-rich manganese-based material is 3 ⁇ m to 6 ⁇ m, and the Dv90 of the lithium-rich manganese-based material is 15 ⁇ m to 20 ⁇ m.
  • the carbon nanotubes based on the total weight of the positive electrode paste, the carbon nanotubes
  • the weight content of the tube is 0.01 wt% to 3 wt% (e.g., 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 3 wt%).
  • the weight content of the carbon nanotubes is 0.01 wt % to 0.5 wt %.
  • the weight content of the lithium-rich manganese-based material is 90wt% to 99.8wt% (for example, 90wt%, 93wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 99.8wt%)
  • the weight content of the conductive material is 0.1wt% to 5wt% (for example, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 5wt%).
  • the weight content of the lithium-rich manganese-based material is 92 wt % to 98 wt %, and the weight content of the conductive material is 1 wt % to 4 wt %.
  • the positive electrode paste includes a binder.
  • the binder includes one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyhexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate and polytetrafluoroethylene.
  • the weight content of the binder is 0.1 wt % to 5 wt %.
  • the weight content of the binder is 1 wt % to 4 wt %.
  • the positive electrode sheet can be prepared by the following method:
  • the slurry is evenly coated on one side or both sides of the positive electrode current collector to form a positive electrode paste.
  • the solvent includes one or more of N-methylpyrrolidone (NMP), N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
  • NMP N-methylpyrrolidone
  • DMF N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • the solid content of the slurry is 67 wt % to 71.5 wt %.
  • the viscosity of the slurry is 3000 Pa ⁇ s to 12000 Pa ⁇ s.
  • a second aspect of the present disclosure provides a battery, comprising the positive electrode sheet described in the first aspect of the present disclosure.
  • the materials of the battery except the positive electrode plate can be prepared according to the methods in the art, and can achieve the effects of high energy density, high cycle stability and high rate performance.
  • the battery may be a lithium ion battery.
  • the battery cell may have a laminate structure or a wound structure.
  • the battery disclosed herein includes the positive electrode sheet disclosed herein, the energy density of the battery is improved, the cycle stability is improved, and the rate performance is improved.
  • Positive electrode current collector aluminum foil
  • Conductive material carbon nanotube (single-walled carbon nanotube, wherein the tube diameter is 1.5 nm, the length is 5000 nm, and the aspect ratio is 2000) 0.06 parts by weight, conductive agent (conductive carbon black) 1.24 parts by weight;
  • Binder PVDF, 1.1 parts by weight.
  • Example group is carried out with reference to Example 1, except that the specific selection of carbon nanotubes is changed, as shown in Tables 1-1 and 1-2.
  • This example group is carried out with reference to Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is changed, see Tables 1-1 and 1-2 for details.
  • This example group was carried out with reference to Example 1, except that the weight ratio of the carbon nanotubes to the conductive agent was changed, as shown in Tables 1-1 and 1-2.
  • This embodiment group is carried out with reference to embodiment 1, except that the Dv10, and/or Dv90, and/or Dv50, and/or specific surface area of the lithium-rich manganese-based material are changed, see Tables 1-1 and 1-2 for details.
  • This embodiment group is carried out with reference to the embodiment 1, except that the tap density of the lithium-rich manganese-based material is changed, see Tables 1-1 and 1-2 for details.
  • Example 2 The process is carried out in accordance with Example 1, except that the particle morphology of the lithium-rich manganese-based material is changed. For details, see Tables 1-1 and 1-2.
  • Example 2 The same method is used as in Example 1, except that the carbon nanotubes are adjusted to the same weight of the conductive agent. For details, see Tables 1-1 and 1-2.
  • Example 2 The same method is carried out as in Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is adjusted to 200:1. For details, see Tables 1-1 and 1-2.
  • Example 2 The same method is used as in Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is adjusted to 3 ⁇ 10 4 :1. For details, see Tables 1-1 and 1-2.
  • Table 1-2 A represents the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube; B represents the ratio of the weight of carbon nanotubes to the weight of the conductive agent; *Same as Example 1; / indicates non-existence.
  • the positive electrode sheets obtained in the embodiment and the comparative example were used to prepare batteries in the following manners.
  • the negative electrode active material artificial graphite, 95 parts by weight
  • the binder SBR, 2 parts by weight
  • the thickener sodium carboxymethyl cellulose, 1.5 parts by weight
  • the conductive agent conductive carbon black, 1.5 parts by weight
  • a solvent deionized water
  • the negative electrode slurry is evenly coated on the surfaces of both sides of the negative electrode collector (copper foil), dried, and compacted by a roller press to obtain a negative electrode sheet.
  • a Z-shaped stack is used to form a bare cell, and the aluminum tabs and the copper-plated nickel tabs are respectively turned out.
  • the bare cell is clamped with a glass clamp with a strength of 100MPa/ m2 , and vacuum-baked at 85°C for 24 hours, and then encapsulated with an aluminum-plastic film.
  • the battery is formed and aged to obtain a square soft-package battery with a length, width and thickness of 60mm ⁇ 40mm ⁇ 5mm. Among them, the design capacity of the battery cell is 4000mAh.
  • the cycling stability can be characterized by the capacity retention after 300 cycles.
  • 300T capacity retention rate At room temperature 25°C, first charge at 1C constant current to 4.4V, then charge at constant voltage. The cut-off current is 0.05C, and the final 1C constant current discharge is performed to 2.5V. The test is repeated in this way until 300 cycles are performed. The ratio of the capacity at this time to the capacity of the first cycle is calculated and recorded as the capacity retention rate.
  • the test was carried out using a two-probe method.
  • the electrode was placed under the probe of a resistance tester at 25°C, the probe was pressed against the electrode at a pressure of 0.4 MPa, and then current was applied for testing.
  • the ratio of the battery capacity (mAh) at the first 0.33C discharge to the mass (g) of the lithium-rich manganese-based material is the ratio of the battery capacity (mAh) at the first 0.33C discharge to the mass (g) of the lithium-rich manganese-based material.
  • the rate performance can be characterized by the 2C discharge capacity retention rate.
  • 2C discharge capacity retention rate At 25°C, the battery is discharged to 2.5V at 0.33C, then charged to 4.4V at 0.33C, and discharged to 2.5V at 0.33C again. The discharge capacity is C0. The battery is charged to 4.4V at 2C, then discharged to 2.5V at 2C. The discharge capacity is C1. The capacity retention rate is calculated as C1/C0*100%.

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Abstract

A positive electrode sheet and a battery comprising same. The positive electrode sheet comprises a positive electrode current collector and a positive electrode paste located on one side surface or two side surfaces of the positive electrode current collector; the positive electrode paste comprises a lithium-rich manganese-based material and a conductive material; the conductive material comprises a carbon nanotube and a conductive agent; the ratio of the median particle diameter Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (233-2.6×104):1. The positive electrode sheet has good conductivity, a high capacity per gram, high cycle stability, a high battery energy density, and high rate performance.

Description

正极片以及包括该正极片的电池Positive electrode sheet and battery including the same 技术领域Technical Field

本公开属于电池技术领域，具体涉及一种正极片以及包括该正极片的电池。The present disclosure belongs to the technical field of batteries, and in particular relates to a positive electrode sheet and a battery including the positive electrode sheet.

背景技术Background Art

为了解决新能源汽车的里程焦虑问题，行业内针对其动力电池的能量密度和快充性能要求也日益提高。在动力电池各组件中，电池正极对电池的循环寿命和能量密度具有重要影响。然而，现有的商业化正极难以满足未来产业对动力电池更高的性能需求，因此，发明一种高能量密度、高循环稳定性能和高倍率性能的电池非常重要。In order to solve the mileage anxiety problem of new energy vehicles, the industry's requirements for the energy density and fast charging performance of its power batteries are also increasing. Among the various components of the power battery, the battery positive electrode has an important impact on the battery's cycle life and energy density. However, the existing commercial positive electrode is difficult to meet the future industry's higher performance requirements for power batteries. Therefore, it is very important to invent a battery with high energy density, high cycle stability and high rate performance.

发明内容Summary of the invention

在锂离子电池正极的活性物质中，富锂锰基材料具有较高的理论克容量(>250mAh/g)和充电电压(≥4.5V)，因此成为高能量密度电池的候选材料。然而，由于富锂锰的离子导电性和电子导电性差，其倍率性能也较为有限。其较差的结构稳定性，和较低的锂离子扩散系数和电子导电性，都影响了使用富锂锰基材料的电池的循环寿命和倍率性能。Among the active materials in the positive electrode of lithium-ion batteries, lithium-rich manganese-based materials have high theoretical gram capacity (>250mAh/g) and charging voltage (≥4.5V), making them candidate materials for high energy density batteries. However, due to the poor ionic and electronic conductivity of lithium-rich manganese, its rate performance is also relatively limited. Its poor structural stability, low lithium ion diffusion coefficient and electronic conductivity all affect the cycle life and rate performance of batteries using lithium-rich manganese-based materials.

本公开的目的在于克服上述现有技术中存在的问题，提供一种正极片以及包括该正极片的电池。本公开的正极片的导电性能好，使该正极片克容量发挥高和循环稳定性高；包括本公开正极片的电池能量密度高、循环稳定性高和倍率性能高。The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and provide a positive electrode sheet and a battery including the positive electrode sheet. The positive electrode sheet disclosed in the present invention has good conductivity, so that the positive electrode sheet has high specific capacity and high cycle stability; the battery including the positive electrode sheet disclosed in the present invention has high energy density, high cycle stability and high rate performance.

研究过程中发现，通过提高正极片的导电性能可以提高电池的循环稳定性和倍率性能。During the research, it was found that the battery's cycle stability and rate performance can be improved by improving the conductivity of the positive electrode.

进一步深入研究发现，为了提高正极片的导电性能，可以通过改变正极片 的结构，使正极片具有较高的循环稳定性。经过大量深入研究筛选出了能够提高正极片导电性能的特定结构。Further in-depth research found that in order to improve the conductivity of the positive electrode, the positive electrode can be changed The structure of the positive electrode has a high cycle stability. After a lot of in-depth research, a specific structure that can improve the conductivity of the positive electrode has been selected.

为了实现上述目的，本公开第一方面提供了一种正极片，所述正极片包括正极集流体以及位于所述正极集流体一侧或两侧表面的正极涂膏，所述正极涂膏包括富锂锰基材料和导电材料，所述导电材料包括碳纳米管，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(233～2.6×104):1。In order to achieve the above-mentioned purpose, the first aspect of the present disclosure provides a positive electrode sheet, which includes a positive electrode collector and a positive electrode paste located on one side or both sides of the positive electrode collector, the positive electrode paste includes a lithium-rich manganese-based material and a conductive material, the conductive material includes carbon nanotubes, and the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is (233~2.6×10 4 ):1.

本公开第二方面提供了一种电池，所述电池包括本公开第一方面所述的正极片。A second aspect of the present disclosure provides a battery, comprising the positive electrode sheet described in the first aspect of the present disclosure.

通过上述技术方案，本公开与现有技术相比至少具有以下优势：Through the above technical solution, the present disclosure has at least the following advantages compared with the prior art:

本公开的正极片通过富锂锰基材料与碳纳米管的协同配合，可以使所述正极片在导电剂用量较少的情况下仍然具有较低的极片电阻率和较高的导电性，从而可以提高正极片克容量的发挥，提高电池的能量密度，提升电池的倍率性能和循环稳定性。The positive electrode sheet disclosed in the present invention can have a lower electrode resistivity and a higher conductivity with a lower amount of conductive agent through the synergistic combination of lithium-rich manganese-based materials and carbon nanotubes, thereby improving the gram capacity of the positive electrode sheet, increasing the energy density of the battery, and enhancing the rate performance and cycle stability of the battery.

本公开的其它特点和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present disclosure will be described in detail in the following detailed description.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1所示为本公开正极片的结构示意图(其中，1为正极集流体、2为正极涂膏、21为富锂锰基材料、22为导电材料、221为碳纳米管、222为导电剂、3为隔膜)。FIG1 is a schematic diagram showing the structure of the positive electrode sheet of the present invention (wherein 1 is the positive electrode current collector, 2 is the positive electrode paste, 21 is the lithium-rich manganese-based material, 22 is the conductive material, 221 is the carbon nanotube, 222 is the conductive agent, and 3 is the separator).

图2所示为本公开实施例1正极片的扫描电子显微镜(SEM)图。FIG. 2 is a scanning electron microscope (SEM) image of the positive electrode sheet of Example 1 of the present disclosure.

具体实施方式DETAILED DESCRIPTION

下文将结合具体实施例对本公开做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本公开，而不应被解释为对本公开保护范围的限制。凡基于本公开上述内容所实现的技术均涵盖在本公开旨在保护的范围内。The present disclosure will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary illustrations and explanations of the present disclosure and should not be construed as limiting the scope of protection of the present disclosure. All technologies implemented based on the above content of the present disclosure are included in the scope of protection intended by the present disclosure.

下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施 例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. Unless otherwise specified, the reagents and materials used in the examples can be obtained from commercial sources.

在本公开的描述中，需要说明的是，术语“第一”、“第二”等仅用于描述目的，而并非指示或暗示相对重要性。In the description of the present disclosure, it should be noted that the terms "first", "second", etc. are only used for descriptive purposes and do not indicate or imply relative importance.

本公开第一方面提供了一种正极片，所述正极片包括正极集流体以及位于所述正极集流体一侧或两侧表面的正极涂膏，所述正极涂膏包括富锂锰基材料和导电材料，所述导电材料包括碳纳米管，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(233～2.6×104):1。A first aspect of the present disclosure provides a positive electrode sheet, comprising a positive electrode collector and a positive electrode paste located on one side or both sides of the positive electrode collector, wherein the positive electrode paste comprises a lithium-rich manganese-based material and a conductive material, wherein the conductive material comprises carbon nanotubes, and the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is (233-2.6×10 4 ):1.

如图1所示，所述正极片包括正极集流体1以及位于所述正极集流体1一侧或两侧表面的正极涂膏2，所述正极涂膏2包括富锂锰基材料21和导电材料22，所述导电材料22包括碳纳米管221和导电剂222。碳纳米管的导电性较强，在导电材料中加入碳纳米管可以改善富锂锰基材料导电性差的问题，从而弥补正极片的表层(涂膏中远离正极集流体的一侧)和底层(涂膏中靠近正极集流体的一侧)之间的电流密度差值，改善涂膏的电阻率，同时基于碳纳米管长径比较大的特性，可以在富锂锰基材料之间构建导电网络，从而提高正极片整体电流密度的均一性，降低极化性，提高富锂锰基材料的脱嵌锂的深度，从而提高正极片克容量的发挥，提高电池的能量密度。As shown in FIG1 , the positive electrode sheet includes a positive electrode current collector 1 and a positive electrode paste 2 located on one side or both sides of the positive electrode current collector 1, wherein the positive electrode paste 2 includes a lithium-rich manganese-based material 21 and a conductive material 22, wherein the conductive material 22 includes a carbon nanotube 221 and a conductive agent 222. The carbon nanotube has a strong conductivity, and the addition of the carbon nanotube to the conductive material can improve the problem of poor conductivity of the lithium-rich manganese-based material, thereby compensating for the current density difference between the surface layer (the side of the paste away from the positive electrode current collector) and the bottom layer (the side of the paste close to the positive electrode current collector) of the positive electrode sheet, improving the resistivity of the paste, and at the same time, based on the large aspect ratio of the carbon nanotube, a conductive network can be constructed between the lithium-rich manganese-based materials, thereby improving the uniformity of the overall current density of the positive electrode sheet, reducing polarizability, and increasing the depth of lithium deintercalation of the lithium-rich manganese-based material, thereby improving the performance of the specific capacity of the positive electrode sheet and improving the energy density of the battery.

所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比可以为(233～2.6×104):1(例如，233:1、265:1、3×103:1、3.5×103:1、4×103:1、4.5×103:1、5×103:1、5.5×103:1、6×103:1、6.5×103:1、7×103:1、7.5×103:1、8×103:1、9×103:1、1×104:1、2×104:1、2.5×104:1、2.6×104:1)。当所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比在上述特定范围时，所述碳纳米管可以在富锂锰基材料之间构成三维导电网络，提高正极片的导电性，提高电池的循环稳定性和倍率性能。从图2中可以看出，富锂锰基材料的表面被碳纳米管和其他导电剂均匀包覆，富锂锰基材料之间由碳纳米管形成的导电网络，该导电网络可以提高正极片的导电性，从而提高电池的循环稳定性和倍率性能。当 所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比低于233:1时，碳纳米管在富锂锰基材料之间不易互相接触，不易构成连续的导电通路，从而使正极片的导电性变差；当所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比高于2.6×104:1，由于碳纳米管的分散效果差，容易出现分散不均匀，不能在富锂锰基材料之间形成均匀的导电网络，从而使正极片的导电性较弱。The ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotube may be (233-2.6×10 4 ):1 (for example, 233:1, 265:1, 3×10 3 :1, 3.5×10 3 :1, 4×10 3 :1, 4.5×10 3 :1, 5×10 3 :1, 5.5×10 3 :1, 6×10 3 :1, 6.5×10 3 :1, 7×10 3 :1, 7.5×10 3 :1, 8×10 3 :1, 9×10 3 :1, 1×10 4 :1, 2×10 4 :1, 2.5×10 4 :1 , 2.6×10 4 :1). When the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotubes is within the above-mentioned specific range, the carbon nanotubes can form a three-dimensional conductive network between the lithium-rich manganese-based materials, thereby improving the conductivity of the positive electrode sheet, and improving the cycle stability and rate performance of the battery. As can be seen from Figure 2, the surface of the lithium-rich manganese-based material is uniformly coated with carbon nanotubes and other conductive agents, and the conductive network formed by the carbon nanotubes between the lithium-rich manganese-based materials can improve the conductivity of the positive electrode sheet, thereby improving the cycle stability and rate performance of the battery. When When the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is lower than 233:1, the carbon nanotubes are not easy to contact each other between the lithium-rich manganese-based materials, and it is not easy to form a continuous conductive path, thereby deteriorating the conductivity of the positive electrode sheet; when the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is higher than 2.6×10 4 :1, due to the poor dispersion effect of the carbon nanotubes, uneven dispersion is likely to occur, and a uniform conductive network cannot be formed between the lithium-rich manganese-based materials, thereby making the conductivity of the positive electrode sheet weaker.

在本公开中，通过上述特征的协同配合，可以提高正极片电流密度的均一性，提高正极片克容量发挥，从而提高电池的能量密度，可以提高正极片的导电性，从而提高电池的循环稳定性和倍率性能。In the present disclosure, through the coordinated cooperation of the above-mentioned features, the uniformity of the current density of the positive electrode sheet can be improved, the specific capacity of the positive electrode sheet can be improved, thereby increasing the energy density of the battery, and the conductivity of the positive electrode sheet can be improved, thereby improving the cycle stability and rate performance of the battery.

通过将正极片设计为具有上述特定结构的正极片，已经能够使正极片实现比现有技术更高的克容量发挥、更高的循环稳定性和更高的倍率性能。为了进一步提高效果，可以对其中一个或多个技术特征做进一步优选。By designing the positive electrode sheet to have the above-mentioned specific structure, the positive electrode sheet can achieve higher specific capacity, higher cycle stability and higher rate performance than the prior art. In order to further improve the effect, one or more of the technical features can be further optimized.

在一实例中，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(2.6×103～2.4×104):1。将所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比限定在上述特定范围，可以进一步提高碳纳米管形成的导电网络的导电性能，从而进一步提高电池的循环稳定性和倍率性能。In one example, the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (2.6×10 3 to 2.4×10 4 ): 1. Limiting the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube within the above-mentioned specific range can further improve the conductivity of the conductive network formed by the carbon nanotubes, thereby further improving the cycle stability and rate performance of the battery.

在一实例中，所述碳纳米管的管径为0.5nm～30nm(例如，0.5nm、1nm、5nm、10nm、15nm、20nm、25nm、30nm)。In one example, the diameter of the carbon nanotube is 0.5 nm to 30 nm (eg, 0.5 nm, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm).

在一实例中，所述碳纳米管的长度＜30μm。In one example, the length of the carbon nanotubes is less than 30 μm.

在一实例中，所述碳纳米管的管径为0.5nm～30nm且所述碳纳米管的长度＜30μm。In one example, the diameter of the carbon nanotube is 0.5 nm to 30 nm and the length of the carbon nanotube is less than 30 μm.

在本公开中，碳纳米管的管径和长度可以通过将含样品的分散液至于透射电子显微镜(TEM)下观测得到。In the present disclosure, the diameter and length of the carbon nanotubes can be obtained by observing a dispersion containing a sample under a transmission electron microscope (TEM).

在一实例中，所述碳纳米管包括单壁碳纳米管和/或多壁碳纳米管。In one example, the carbon nanotubes include single-walled carbon nanotubes and/or multi-walled carbon nanotubes.

在一实例中，所述碳纳米管为单壁碳纳米管。由于单壁碳纳米管的结构较简单，化学性质较稳定，而且单壁碳纳米管的长径比相对于多壁碳纳米管来说 比较大，因此采用单壁碳纳米管时，可以用较少量的单壁碳纳米管即可在富锂锰基材料之间形成较好的三维导电网络，从而提高正极片的导电性，提高电池的循环稳定性和倍率性能。In one embodiment, the carbon nanotubes are single-walled carbon nanotubes. Single-walled carbon nanotubes have a simpler structure, more stable chemical properties, and a smaller aspect ratio than multi-walled carbon nanotubes. Therefore, when single-walled carbon nanotubes are used, a relatively small amount of single-walled carbon nanotubes can be used to form a better three-dimensional conductive network between the lithium-rich manganese-based materials, thereby improving the conductivity of the positive electrode sheet and improving the cycle stability and rate performance of the battery.

在一实例中，所述单壁碳纳米管的管径为0.5nm-3nm(例如，0.5nm、1nm、1.5nm、2nm、2.5nm、2.9nm、3nm)，和/或，所述单壁碳纳米管的长度为600nm～8400nm(例如，600nm、1000nm、1500nm、1800nm、2000nm、2500nm、3000nm、3500nm、4000nm、4500nm、5000nm、5500nm、6000nm、6500nm、7000nm、7200nm、7500nm、8000nm、8400nm)，和/或，所述单壁碳纳米管的长径比为(200～16800):1(例如，200:1、500:1、700:1、1000:1、2000:1、3000:1、4000:1、5000:1、6000:1、7000:1、8000:1、9000:1、10000:1、12000:1、15000:1、16800:1)。In one example, the diameter of the single-walled carbon nanotube is 0.5 nm-3 nm (e.g., 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 2.9 nm, 3 nm), and/or the length of the single-walled carbon nanotube is 600 nm-8400 nm (e.g., 600 nm, 1000 nm, 1500 nm, 1800 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, 5500 nm, 6000 nm, 8000 nm, 9000 nm, 10000 nm, 15000 nm, 1800 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, 5500 nm, 6000 nm, 8 ... 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 6500nm, 7000nm, 7200nm, 7500nm, 8000nm, 8400nm), and/or the aspect ratio of the single-walled carbon nanotube is (200-16800):1 (for example, 200:1, 500:1, 700:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, 10000:1, 12000:1, 15000:1, 16800:1).

在一实例中，所述单壁碳纳米管的管径0.5nm～3nm，且所述单壁碳纳米管的长度为600nm～8400nm，且所述单壁碳纳米管的长径比为(200～16800):1。当所述单壁碳纳米管满足上述特定技术特征的限定时，所述单壁碳纳米管可以在浆料中保持均匀的分散而不团聚，并且在涂膏中可以均匀的包覆在富锂锰基材料的表面，从而提高在富锂锰基材料之间的导电网络的导电性，进一步提高正极片的导电性，提高电池的循环稳定性和倍率性能。In one example, the diameter of the single-walled carbon nanotube is 0.5nm-3nm, the length of the single-walled carbon nanotube is 600nm-8400nm, and the aspect ratio of the single-walled carbon nanotube is (200-16800): 1. When the single-walled carbon nanotube meets the above-mentioned specific technical characteristics, the single-walled carbon nanotube can be uniformly dispersed in the slurry without agglomeration, and can be uniformly coated on the surface of the lithium-rich manganese-based material in the paste, thereby improving the conductivity of the conductive network between the lithium-rich manganese-based materials, further improving the conductivity of the positive electrode sheet, and improving the cycle stability and rate performance of the battery.

在一实例中，所述单壁碳纳米管的管径为0.5nm-3nm(例如，0.5nm、0.7nm、1nm、1.2nm、1.5nm、1.7nm、2nm、2.2nm、2.5nm、2.7nm、3nm)，和/或，所述单壁碳纳米管的长度为3000nm～6000nm(例如，3000nm、3500nm、4000nm、4500nm、5000nm、5500nm、6000nm)，和/或，所述单壁碳纳米管的长径比为(1000～12000):1(例如，1000:1、3000:1、5000:1、7000:1、10000:1、12000:1)。In one example, the diameter of the single-walled carbon nanotube is 0.5nm-3nm (for example, 0.5nm, 0.7nm, 1nm, 1.2nm, 1.5nm, 1.7nm, 2nm, 2.2nm, 2.5nm, 2.7nm, 3nm), and/or the length of the single-walled carbon nanotube is 3000nm-6000nm (for example, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, 5500nm, 6000nm), and/or the aspect ratio of the single-walled carbon nanotube is (1000-12000):1 (for example, 1000:1, 3000:1, 5000:1, 7000:1, 10000:1, 12000:1).

在一实例中，所述导电材料还包括导电剂。In one example, the conductive material further includes a conductive agent.

根据一种具体的实施方式，所述碳纳米管的重量与所述导电剂的重量之比 为(0.002～1.5):1。当碳纳米管的重量与所述导电剂的重量之比低于0.002:1时，碳纳米管太少将不利于构建三维导电网络；当碳纳米管的重量与所述导电剂的重量之比高于1.5:1时，过多的碳纳米管容易发生团聚，使其分散不均匀。当碳纳米管的重量与所述导电剂的重量之比在上述特定范围时，能够在保持均匀分散的同时形成良好的导电网络，从而提升极片的导电性能。According to a specific embodiment, the weight ratio of the carbon nanotubes to the conductive agent is (0.002-1.5):1. When the weight ratio of carbon nanotubes to the weight of the conductive agent is lower than 0.002:1, too few carbon nanotubes will be unfavorable for building a three-dimensional conductive network; when the weight ratio of carbon nanotubes to the weight of the conductive agent is higher than 1.5:1, too many carbon nanotubes are prone to agglomeration, making them unevenly dispersed. When the weight ratio of carbon nanotubes to the weight of the conductive agent is within the above-mentioned specific range, a good conductive network can be formed while maintaining uniform dispersion, thereby improving the conductive performance of the electrode.

在一实例中，所述碳纳米管的重量与所述导电剂的重量之比为(0.002～0.14):1。In one example, the weight ratio of the carbon nanotubes to the conductive agent is (0.002-0.14):1.

在一实例中，所述导电材料还包括导电剂，所述导电剂包括导电炭黑(如科琴黑、乙炔黑、KS-6、KS-15、S-O)、碳纤维和石墨烯(如SEG-6)中的一种或多种。In one example, the conductive material further includes a conductive agent, which includes one or more of conductive carbon black (such as Ketjen black, acetylene black, KS-6, KS-15, S-O), carbon fiber and graphene (such as SEG-6).

在一实例中，所述富锂锰基材料的化学式为xLi2MnO3·(1-x)LiMzNyO2。在化学式xLi2MnO3·(1-x)LiMzNyO2中各元素之间符合化合物中各种元素的正负化合价代数和为零的原则。In one example, the chemical formula of the lithium-rich manganese-based material is xLi 2 MnO 3 ·(1-x)LiM z N y O 2 . In the chemical formula xLi 2 MnO 3 ·(1-x)LiM z N y O 2 , the elements comply with the principle that the algebraic sum of positive and negative valences of the elements in the compound is zero.

其中，0＜x＜1。x可以为小数，例如，x为0.1、0.122、0.2、0.243、0.3、0.4、0.45、0.5、0.6、0.7、0.8、0.9。Wherein, 0＜x＜1. x can be a decimal, for example, x is 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.

其中，0≤y＜1。y可以为小数，例如，y为0、0.1、0.122、0.2、0.243、0.3、0.4、0.45、0.5、0.6、0.7、0.8、0.9。Wherein, 0≤y＜1. y can be a decimal, for example, y is 0, 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.

其中，0≤z＜1。y可以为小数，例如，y为0、0.1、0.122、0.2、0.243、0.3、0.4、0.45、0.5、0.6、0.7、0.8、0.9。Wherein, 0≤z＜1. y can be a decimal, for example, y is 0, 0.1, 0.122, 0.2, 0.243, 0.3, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9.

M可以包括Ni、Co和Mn中的一种或多种。当M为多种元素时，多种元素的原子数之和为z。例如，M为Ni和Mn时，Ni的原子数与Mn的原子数之和为z。M may include one or more of Ni, Co and Mn. When M is a plurality of elements, the sum of the atomic numbers of the plurality of elements is z. For example, when M is Ni and Mn, the sum of the atomic number of Ni and the atomic number of Mn is z.

N可以包括过渡金属元素，优选地N包括Al、Cr、Nb、Mg、Mo、Ta和V中的一种或多种。当N为多种元素时，多种元素的原子数之和为y。例如，N为Al和Nb时，Al的原子数与Nb的原子数之和为y。N may include transition metal elements, preferably N includes one or more of Al, Cr, Nb, Mg, Mo, Ta and V. When N is a plurality of elements, the sum of the atomic numbers of the plurality of elements is y. For example, when N is Al and Nb, the sum of the atomic number of Al and the atomic number of Nb is y.

在一实例中，所述富锂锰基材料的比表面积为1m2/g～4m2/g(例如，1m2/g、1.2m2/g、1.5m2/g、2m2/g、2.5m2/g、3m2/g、3.2m2/g、4m2/g)。 In one example, the specific surface area of the lithium-rich manganese-based material is 1 m 2 /g to 4 m 2 /g (e.g., 1 m 2 /g, 1.2 m 2 /g, 1.5 m 2 /g, 2 m 2 /g, 2.5 m 2 /g, 3 m 2 /g, 3.2 m 2 /g, 4 m 2 /g).

在一实例中，所述富锂锰基材料的比表面积为1.5m2/g～3m2/g。当所述富锂锰基材料比表面积控制在上述范围内时，可保证正极活性物质与电解液之间充分接触，以具备良好的脱嵌锂能力，同时也不会因接触面积过大而产生较为严重的副反应。In one example, the specific surface area of the lithium-rich manganese-based material is 1.5 m 2 /g to 3 m 2 /g. When the specific surface area of the lithium-rich manganese-based material is controlled within the above range, sufficient contact between the positive electrode active material and the electrolyte can be ensured to have good lithium insertion and extraction capabilities, while no serious side reactions will occur due to excessive contact area.

在一实例中，所述富锂锰基材料的振实密度为1g/cm3～3g/cm3(例如，1g/cm3、1.2g/cm3、1.5g/cm3、1.7g/cm3、2g/cm3、2.5g/cm3、3g/cm3)。In one example, the tap density of the lithium-rich manganese-based material is 1 g/cm 3 to 3 g/cm 3 (eg, 1 g/cm 3 , 1.2 g/cm 3 , 1.5 g/cm 3 , 1.7 g/cm 3 , 2 g/cm 3 , 2.5 g/cm 3 , 3 g/cm 3 ).

在一实例中，所述富锂锰基材料的振实密度为1.2g/cm3～2g/cm3。当富锂锰基材料的振实密度控制在上述范围内时，可以有效提高正极极片内部空间利用率，并保证活性物质与导电材料之间充分接触，提高极片导电性能。In one example, the tap density of the lithium-rich manganese-based material is 1.2 g/cm 3 to 2 g/cm 3 . When the tap density of the lithium-rich manganese-based material is controlled within the above range, the internal space utilization of the positive electrode plate can be effectively improved, and sufficient contact between the active material and the conductive material can be ensured, thereby improving the conductive performance of the plate.

在一实例中，所述富锂锰基材料包括多晶结构。所述“多晶结构”是指每个活性材料颗粒本身是由多个粒径较小的一次颗粒晶体团聚而成。In one example, the lithium-rich manganese-based material includes a polycrystalline structure. The “polycrystalline structure” means that each active material particle itself is formed by the aggregation of multiple primary particle crystals with smaller particle sizes.

根据一种具体的实施方式，所述富锂锰基材料的中值粒径Dv50为7μm～13μm(例如，7μm、7.5μm、8μm、8.5μm、9μm、9.5μm、10μm、10.5μm、11.5μm、12μm、12.5μm、13μm)。通过将材料Dv50控制在上述范围内，可以保持富锂锰基材料颗粒均匀分散，提高空间利用率，并与导电材料(包括碳纳米管和其他导电剂)均匀接触，形成均一、良好的导电网络，以提高正极整体的导电性能。According to a specific embodiment, the median particle size Dv50 of the lithium-rich manganese-based material is 7 μm to 13 μm (for example, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm). By controlling the material Dv50 within the above range, the lithium-rich manganese-based material particles can be kept uniformly dispersed, the space utilization rate can be improved, and the lithium-rich manganese-based material particles can be uniformly contacted with the conductive material (including carbon nanotubes and other conductive agents) to form a uniform and good conductive network to improve the overall conductivity of the positive electrode.

在一实例中，所述富锂锰基材料的中值粒径Dv50为8μm～12μm。In one example, the median particle size Dv50 of the lithium-rich manganese-based material is 8 μm to 12 μm.

根据一种具体的实施方式，所述富锂锰基材料的Dv10为1μm～7μm(例如，1μm、2μm、3μm、4μm、5μm、6μm、7μm)。通过将材料Dv10控制在上述范围内，可以保持富锂锰基材料颗粒均匀分散，提高空间利用率，并与导电材料(包括碳纳米管和其他导电剂)均匀接触，形成均一、良好的导电网络，以提高正极整体的导电性能。According to a specific embodiment, the Dv10 of the lithium-rich manganese-based material is 1 μm to 7 μm (for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm). By controlling the material Dv10 within the above range, the lithium-rich manganese-based material particles can be kept uniformly dispersed, the space utilization rate can be improved, and the conductive material (including carbon nanotubes and other conductive agents) can be uniformly contacted to form a uniform and good conductive network to improve the overall conductivity of the positive electrode.

在一实例中，富锂锰基材料的Dv10为3μm～6μm。In one example, the Dv10 of the lithium-rich manganese-based material is 3 μm to 6 μm.

根据一种具体的实施方式，所述富锂锰基材料的Dv90为13μm～23μm(例如， 13μm、15μm、15.5μm、16μm、16.5μm、17μm、17.5μm、18μm、18.5μm、19μm、19.5μm、20μm、20.5μm、21μm、21.5μm、22μm、22.5μm、23μm)。通过将材料Dv90控制在上述范围内，可以保持富锂锰基材料颗粒均匀分散，提高空间利用率，并与导电材料(包括碳纳米管和其他导电剂)均匀接触，形成均一、良好的导电网络，以提高正极整体的导电性能。According to a specific embodiment, the Dv90 of the lithium-rich manganese-based material is 13 μm to 23 μm (for example, By controlling the Dv90 of the material within the above range, the lithium-rich manganese-based material particles can be uniformly dispersed, the space utilization rate can be improved, and the lithium-rich manganese-based material particles can be uniformly contacted with the conductive material (including carbon nanotubes and other conductive agents) to form a uniform and good conductive network, so as to improve the overall conductive performance of the positive electrode.

在一实例中，所述富锂锰基材料的Dv90为15μm～20μm。In one example, the Dv90 of the lithium-rich manganese-based material is 15 μm to 20 μm.

在本公开中，中值粒径Dv50、Dv10和Dv90可以通过粒度分析仪测试得到。DvN(如Dv10、Dv50、Dv90)指的是一个样品的累计体积粒度分布百分数达到N％时所对应的粒径。具体的，Dv10：颗粒累积分布为10％的粒径，即小于等于此粒径的颗粒体积含量占全部颗粒的10％；Dv50：颗粒累积分布为10％的粒径，即小于等于此粒径的颗粒体积含量占全部颗粒的50％；Dv90：颗粒累积分布为90％的粒径，即小于等于此粒径的颗粒体积含量占全部颗粒的90％。In the present disclosure, the median particle sizes Dv50, Dv10 and Dv90 can be obtained by testing with a particle size analyzer. DvN (such as Dv10, Dv50, Dv90) refers to the particle size corresponding to when the cumulative volume particle size distribution percentage of a sample reaches N%. Specifically, Dv10: the particle size at which the cumulative distribution of particles is 10%, that is, the volume content of particles less than or equal to this particle size accounts for 10% of all particles; Dv50: the particle size at which the cumulative distribution of particles is 10%, that is, the volume content of particles less than or equal to this particle size accounts for 50% of all particles; Dv90: the particle size at which the cumulative distribution of particles is 90%, that is, the volume content of particles less than or equal to this particle size accounts for 90% of all particles.

在一实例中，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(233～2.6×104):1，且所述富锂锰基材料的中值粒径Dv50为7μm～13μm，所述富锂锰基材料的Dv10为1μm～7μm，所述富锂锰基材料的Dv90为13μm～23μm。通过上述特定富锂锰基材料与碳纳米管的协同配合，可以保证富锂锰基材料颗粒均匀分散，提高空间利用率，实现富锂锰基材料与碳纳米管的较好搭配，形成均一、良好的导电网络，进一步提高导电网络的导电性能。In one example, the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (233-2.6×10 4 ): 1, and the median particle size Dv50 of the lithium-rich manganese-based material is 7μm-13μm, the Dv10 of the lithium-rich manganese-based material is 1μm-7μm, and the Dv90 of the lithium-rich manganese-based material is 13μm-23μm. Through the synergistic combination of the above-mentioned specific lithium-rich manganese-based material and carbon nanotubes, the lithium-rich manganese-based material particles can be uniformly dispersed, the space utilization rate can be improved, the lithium-rich manganese-based material and the carbon nanotubes can be better matched, a uniform and good conductive network can be formed, and the conductive performance of the conductive network can be further improved.

在一实例中，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(2.8×103～2.4×104):1，且所述富锂锰基材料的中值粒径Dv50为8μm～12μm，所述富锂锰基材料的Dv10为3μm～6μm，所述富锂锰基材料的Dv90为15μm～20μm。通过上述特定富锂锰基材料与碳纳米管的协同配合，可以保证富锂锰基材料颗粒均匀分散，提高空间利用率，实现富锂锰基材料与碳纳米管的更好搭配，形成更均一、更好的导电网络，进一步提高导电网络的导电性能。In one example, the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is (2.8×10 3 to 2.4×10 4 ): 1, and the median particle size Dv50 of the lithium-rich manganese-based material is 8μm to 12μm, the Dv10 of the lithium-rich manganese-based material is 3μm to 6μm, and the Dv90 of the lithium-rich manganese-based material is 15μm to 20μm. Through the synergistic combination of the above-mentioned specific lithium-rich manganese-based material and carbon nanotubes, it is possible to ensure that the lithium-rich manganese-based material particles are evenly dispersed, improve space utilization, achieve better matching of the lithium-rich manganese-based material and the carbon nanotubes, form a more uniform and better conductive network, and further improve the conductive performance of the conductive network.

根据一种具体的实施方式，以所述正极涂膏的总重量为基准，所述碳纳米 管的重量含量为0.01wt％～3wt％(例如，0.01wt％、0.05wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、3wt％)。According to a specific embodiment, based on the total weight of the positive electrode paste, the carbon nanotubes The weight content of the tube is 0.01 wt% to 3 wt% (e.g., 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 3 wt%).

在一实例中，以所述正极涂膏的总重量为基准，所述碳纳米管的重量含量为0.01wt％～0.5wt％。In one example, based on the total weight of the positive electrode paste, the weight content of the carbon nanotubes is 0.01 wt % to 0.5 wt %.

根据一种具体的实施方式，以所述正极涂膏的总重量为基准，所述富锂锰基材料的重量含量为90wt％～99.8wt％(例如，90wt％、93wt％、95wt％、96wt％、97wt％、98wt％、99wt％、99.8wt％)，所述导电材料的重量含量为0.1wt％～5wt％(例如，0.1wt％、0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、5wt％)。According to a specific embodiment, based on the total weight of the positive electrode paste, the weight content of the lithium-rich manganese-based material is 90wt% to 99.8wt% (for example, 90wt%, 93wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 99.8wt%), and the weight content of the conductive material is 0.1wt% to 5wt% (for example, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 5wt%).

在一实例中，以所述正极涂膏的总重量为基准，所述富锂锰基材料的重量含量为92wt％～98wt％，所述导电材料的重量含量为1wt％～4wt％。In one example, based on the total weight of the positive electrode paste, the weight content of the lithium-rich manganese-based material is 92 wt % to 98 wt %, and the weight content of the conductive material is 1 wt % to 4 wt %.

在一实例中，所述正极涂膏包括粘结剂。In one example, the positive electrode paste includes a binder.

在一实例中，所述粘结剂包括聚偏氟乙烯、聚偏氟乙烯－六氟丙烯的共聚物、聚六氟丙烯、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯吡咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯和聚四氟乙烯中的一种或多种。In one example, the binder includes one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyhexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate and polytetrafluoroethylene.

在一实例中，以所述正极涂膏的总重量为基准，所述粘结剂的重量含量为0.1wt％～5wt％。In one example, based on the total weight of the positive electrode paste, the weight content of the binder is 0.1 wt % to 5 wt %.

在一实例中，所述正极涂膏的总重量为基准，所述粘结剂的重量含量为1wt％～4wt％。In one example, based on the total weight of the positive electrode paste, the weight content of the binder is 1 wt % to 4 wt %.

所述正极片可以通过以下方法制备得到：The positive electrode sheet can be prepared by the following method:

(1)将粘结剂、导电材料(包括碳纳米管和导电剂)与溶剂混合，置于搅拌罐中至少搅拌60min使制得的胶液均匀即可；(1) mixing a binder, a conductive material (including carbon nanotubes and a conductive agent) and a solvent, and placing the mixture in a stirring tank and stirring for at least 60 minutes to make the obtained adhesive solution uniform;

(2)将富锂锰基材料和所述胶液混合，搅拌60min～80min后使浆料分散均匀即可；(2) mixing the lithium-rich manganese-based material and the glue solution, and stirring for 60 to 80 minutes until the slurry is evenly dispersed;

(3)将所述浆料均匀地涂在正极集流体一侧或两侧，形成正极涂膏。 (3) The slurry is evenly coated on one side or both sides of the positive electrode current collector to form a positive electrode paste.

在一实例中，所述溶剂包括N-甲基吡咯烷酮(NMP)、N-二甲基酰胺(DMF)、二甲基亚砜(DMSO)中的一种或多种。In one example, the solvent includes one or more of N-methylpyrrolidone (NMP), N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

在一实例中，所述浆料的固体含量为67wt％～71.5wt％。In one example, the solid content of the slurry is 67 wt % to 71.5 wt %.

在一实例中，所述浆料的粘度为3000Pa·s～12000Pa·s。In one example, the viscosity of the slurry is 3000 Pa·s to 12000 Pa·s.

本公开第二方面提供了一种电池，所述电池包括本公开第一方面所述的正极片。A second aspect of the present disclosure provides a battery, comprising the positive electrode sheet described in the first aspect of the present disclosure.

所述电池除正极片以为的材料均可以按照本领域的方式进行，均能实现能量密度高、循环稳定性高和倍率性能高的效果。The materials of the battery except the positive electrode plate can be prepared according to the methods in the art, and can achieve the effects of high energy density, high cycle stability and high rate performance.

所述电池可以为锂离子电池。The battery may be a lithium ion battery.

所述电池的电芯可以为叠片结构或卷绕结构。The battery cell may have a laminate structure or a wound structure.

本公开的电池由于包括本公开所述的正极片，电池的能量密度提升，循环稳定性提高，倍率性能提高。Since the battery disclosed herein includes the positive electrode sheet disclosed herein, the energy density of the battery is improved, the cycle stability is improved, and the rate performance is improved.

以下将通过实施例对本公开进行详细描述。本公开所描述的实施例仅是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。The present disclosure will be described in detail below through embodiments. The embodiments described in the present disclosure are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present disclosure.

以下实施例用于说明本公开的正极片The following examples are used to illustrate the positive electrode sheet disclosed in the present invention.

实施例1Example 1

(1)成分准备(1) Preparation of ingredients

正极集流体：铝箔；Positive electrode current collector: aluminum foil;

富锂锰基材料97.6重量份；97.6 parts by weight of lithium-rich manganese-based material;

导电材料：碳纳米管(单壁碳纳米管，其中，管径1.5nm，长度5000nm，长径比为2000)0.06重量，导电剂(导电炭黑)1.24重量份；Conductive material: carbon nanotube (single-walled carbon nanotube, wherein the tube diameter is 1.5 nm, the length is 5000 nm, and the aspect ratio is 2000) 0.06 parts by weight, conductive agent (conductive carbon black) 1.24 parts by weight;

粘结剂：PVDF，1.1重量份。Binder: PVDF, 1.1 parts by weight.

(2)正极片的制备 (2) Preparation of positive electrode

1)将粘结剂、导电材料(包括碳纳米管和导电剂)与溶剂混合，置于搅拌罐中搅拌60min使制得的胶液均匀；1) Mixing a binder, a conductive material (including carbon nanotubes and a conductive agent) and a solvent, placing the mixture in a stirring tank and stirring for 60 minutes to make the obtained glue solution uniform;

2)将富锂锰基材料和所述胶液混合，搅拌60min后使浆料分散均匀；2) mixing the lithium-rich manganese-based material and the glue, and stirring for 60 minutes to make the slurry evenly dispersed;

3)将所述浆料均匀地涂在正极集流体的两侧表面，形成正极涂膏，然后经辊压、分切得到正极片。3) The slurry is evenly coated on both sides of the positive electrode current collector to form a positive electrode paste, which is then rolled and cut to obtain a positive electrode sheet.

实施例2Example 2

本实施例组参照实施例1进行，所不同的是，改变碳纳米管的具体选择，具体参见表1-1和1-2。This example group is carried out with reference to Example 1, except that the specific selection of carbon nanotubes is changed, as shown in Tables 1-1 and 1-2.

实施例3组Example 3 Group

本实施例组参照实施例1进行，所不同的是，改变富锂锰基材料的中值粒径Dv50与碳纳米管的管径之比，具体参见表1-1和1-2。This example group is carried out with reference to Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is changed, see Tables 1-1 and 1-2 for details.

实施例4组Example 4 Group

本实施例组参照实施例1进行，所不同的是，改变碳纳米管的重量与导电剂的重量之比，具体参见表1-1和1-2。This example group was carried out with reference to Example 1, except that the weight ratio of the carbon nanotubes to the conductive agent was changed, as shown in Tables 1-1 and 1-2.

实施例5组Example 5 Group

本组实施例组参照实施例1进行，所不同的是，改变单壁碳纳米管的长度或长径比，具体参见表1-1和1-2。This group of examples is carried out with reference to Example 1, except that the length or aspect ratio of the single-walled carbon nanotubes is changed, as shown in Tables 1-1 and 1-2.

实施例6组Example 6 Group

本实施例组参照实施例1进行，所不同的是，改变富锂锰基材料的Dv10，和/或，Dv90，和/或Dv50，和/或比表面积，具体参见表1-1和1-2。 This embodiment group is carried out with reference to embodiment 1, except that the Dv10, and/or Dv90, and/or Dv50, and/or specific surface area of the lithium-rich manganese-based material are changed, see Tables 1-1 and 1-2 for details.

实施例7组Example 7 Group

本实施例组参照实施例1进行，所不同的是，改变富锂锰基材料的振实密度，具体参见表1-1和1-2。This embodiment group is carried out with reference to the embodiment 1, except that the tap density of the lithium-rich manganese-based material is changed, see Tables 1-1 and 1-2 for details.

实施例8Example 8

参照实施例1进行，所不同的是，改变富锂锰基材料的颗粒形貌，具体参见表1-1和1-2。The process is carried out in accordance with Example 1, except that the particle morphology of the lithium-rich manganese-based material is changed. For details, see Tables 1-1 and 1-2.

对比例1Comparative Example 1

参照实施例1进行，所不同的是，将碳纳米管调整为相同重量份的导电剂，具体参见表1-1和1-2。The same method is used as in Example 1, except that the carbon nanotubes are adjusted to the same weight of the conductive agent. For details, see Tables 1-1 and 1-2.

对比例2Comparative Example 2

参见实施例1进行，所不同的是，将富锂锰基材料的中值粒径Dv50与碳纳米管的管径之比调整为200:1，具体参见表1-1和1-2。The same method is carried out as in Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is adjusted to 200:1. For details, see Tables 1-1 and 1-2.

对比例3Comparative Example 3

参见实施例1进行，所不同的是，将富锂锰基材料的中值粒径Dv50与碳纳米管的管径之比调整为3×104:1，具体参见表1-1和1-2。The same method is used as in Example 1, except that the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube is adjusted to 3×10 4 :1. For details, see Tables 1-1 and 1-2.

表1-1

Table 1-1

表1-2


A表示富锂锰基材料的中值粒径Dv50与碳纳米管的管径之比；
B表示碳纳米管的重量与导电剂的重量之比；
*表示同实施例1；
/表示不存在。 Table 1-2


A represents the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the diameter of the carbon nanotube;
B represents the ratio of the weight of carbon nanotubes to the weight of the conductive agent;
*Same as Example 1;
/ indicates non-existence.

制备例Preparation Example

将实施例和对比例所得的正极片分别按照以下方式制备电池。The positive electrode sheets obtained in the embodiment and the comparative example were used to prepare batteries in the following manners.

(1)正极片(1) Positive electrode

分别使用上述各实施例和对比例所得的正极片。The positive electrode sheets obtained in the above-mentioned embodiments and comparative examples were used respectively.

(2)负极片(2) Negative electrode

将负极活性物质(人造石墨，95重量份)、粘结剂(SBR类，2重量份)、增稠剂(羧甲基纤维素钠，1.5重量份)和导电剂(导电炭黑，1.5重量份)混合，经高速搅拌得到分散均匀的含有负极活性物质的混合物，加入溶剂(去离子水)，制成负极浆料，其中所述负极浆料中固含量为50wt％。将所述负极浆料均匀地涂在负极集流体(铜箔)两侧表面，经过干燥、辊压机压实，得到负极片。The negative electrode active material (artificial graphite, 95 parts by weight), the binder (SBR, 2 parts by weight), the thickener (sodium carboxymethyl cellulose, 1.5 parts by weight) and the conductive agent (conductive carbon black, 1.5 parts by weight) are mixed, stirred at high speed to obtain a uniformly dispersed mixture containing the negative electrode active material, and a solvent (deionized water) is added to prepare a negative electrode slurry, wherein the solid content in the negative electrode slurry is 50wt%. The negative electrode slurry is evenly coated on the surfaces of both sides of the negative electrode collector (copper foil), dried, and compacted by a roller press to obtain a negative electrode sheet.

(3)电解液(3) Electrolyte

将1mol/L的六氟磷酸锂，与溶剂(体积比为：碳酸乙烯酯：碳酸二甲酯：1,2-丙二醇碳酸酯＝1:1:1)混合，制得电解液。1 mol/L lithium hexafluorophosphate was mixed with a solvent (volume ratio: ethylene carbonate: dimethyl carbonate: 1,2-propylene glycol carbonate = 1:1:1) to prepare an electrolyte.

(4)电池的制备(4) Preparation of batteries

将步骤(2)的负极片和步骤(1)的正极片冲片后，采用Z型叠片形成裸电池，分别转出铝极耳和铜镀镍极耳。将裸电池使用玻璃夹夹紧，玻璃夹的力度为100MPa/m2，并在85℃高温真空烘烤24小时，再用铝塑膜封装。封装后对电池进行化成和老化，得到长宽厚为60mm×40mm×5mm的方形软包装电池。其中，电芯的设计容量为4000mAh。After punching the negative electrode sheet of step (2) and the positive electrode sheet of step (1), a Z-shaped stack is used to form a bare cell, and the aluminum tabs and the copper-plated nickel tabs are respectively turned out. The bare cell is clamped with a glass clamp with a strength of 100MPa/ m2 , and vacuum-baked at 85℃ for 24 hours, and then encapsulated with an aluminum-plastic film. After encapsulation, the battery is formed and aged to obtain a square soft-package battery with a length, width and thickness of 60mm×40mm×5mm. Among them, the design capacity of the battery cell is 4000mAh.

测试例Test Case

对实施例和对比例所得的电池分别进行如下测试：The batteries obtained in the examples and comparative examples were tested as follows:

(1)循环稳定性测试(1) Cyclic stability test

循环稳定性可以通过循环300周的容量保持率表征。The cycling stability can be characterized by the capacity retention after 300 cycles.

300T容量保持率：室温25℃下，首先在1C恒流充电至4.4V，再恒压充电， 截止电流0.05C，最后1C恒流放电至2.5V，如此循环测试，直至循环至300次，并计算此时的容量与首次循环的容量之比，记为容量保持率。300T capacity retention rate: At room temperature 25°C, first charge at 1C constant current to 4.4V, then charge at constant voltage. The cut-off current is 0.05C, and the final 1C constant current discharge is performed to 2.5V. The test is repeated in this way until 300 cycles are performed. The ratio of the capacity at this time to the capacity of the first cycle is calculated and recorded as the capacity retention rate.

(2)极片电阻率的测试(2) Test of electrode resistivity

以两探针法进行测试，在25℃下将极片置于电阻测试仪探针下，将探针以0.4MPa的压力下压极片，随后施加电流进行测试。The test was carried out using a two-probe method. The electrode was placed under the probe of a resistance tester at 25°C, the probe was pressed against the electrode at a pressure of 0.4 MPa, and then current was applied for testing.

(3)克容量发挥的测试(3) Test of gram capacity

电池首次0.33C放电时的容量(mAh)与富锂锰基材料的质量(g)的比值。The ratio of the battery capacity (mAh) at the first 0.33C discharge to the mass (g) of the lithium-rich manganese-based material.

(4)倍率性能测试(4) Rate performance test

倍率性能可以通过2C放电容量保持率表征。The rate performance can be characterized by the 2C discharge capacity retention rate.

2C放电容量保持率：在25℃下，将电池以0.33C放电至2.5V，随后0.33C充电至4.4V，并再次0.33C放电至2.5V，以此放电容量为C0。将电池以2C充电至4.4V，随后2C放电至2.5V，以此放电容量为C1。容量保持率计算方法为C1/C0*100％。2C discharge capacity retention rate: At 25°C, the battery is discharged to 2.5V at 0.33C, then charged to 4.4V at 0.33C, and discharged to 2.5V at 0.33C again. The discharge capacity is C0. The battery is charged to 4.4V at 2C, then discharged to 2.5V at 2C. The discharge capacity is C1. The capacity retention rate is calculated as C1/C0*100%.

将所得结果记于表2中。The obtained results are recorded in Table 2.

表2

Table 2

通过表2可以看出，通过对比例和实施例可以看出，实施例的正极片制得的电池300T容量保持率明显提升，2C放电容量保持率明显提升，极片电阻率明显降低，正极片的克容量提升，说明本公开的正极片以及包括该正极片的电池，通过对富锂锰基材料的中值粒Dv50与碳纳米管的管径之比的限定，提高了电池的循环稳定性和倍率性能，提升了电池的能量密度。It can be seen from Table 2 that, through the comparative examples and the embodiments, it can be seen that the 300T capacity retention rate of the battery made from the positive electrode sheet of the embodiment is significantly improved, the 2C discharge capacity retention rate is significantly improved, the electrode sheet resistivity is significantly reduced, and the gram capacity of the positive electrode sheet is improved, indicating that the positive electrode sheet of the present invention and the battery including the positive electrode sheet, by limiting the ratio of the median particle Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes, improves the cycle stability and rate performance of the battery, and improves the energy density of the battery.

以上详细描述了本公开的优选实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内容，均属于本公开的保护范围。The preferred embodiments of the present disclosure are described in detail above, but the present disclosure is not limited thereto. Within the technical concept of the present disclosure, the technical solution of the present disclosure can be subjected to a variety of simple modifications, including combining various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present disclosure and belong to the protection scope of the present disclosure.

以上，对本公开的实施方式进行了说明。但是，本公开不限定于上述实施方式。凡在本公开的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。 The above describes the implementation methods of the present disclosure. However, the present disclosure is not limited to the above implementation methods. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present disclosure shall be included in the protection scope of the present disclosure.

Claims (15)

一种正极片，其特征在于，所述正极片包括正极集流体以及位于所述正极集流体一侧或两侧表面的正极涂膏，所述正极涂膏包括富锂锰基材料和导电材料，所述导电材料包括碳纳米管，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(233～2.6×104):1。A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode paste located on one side or both sides of the positive electrode current collector, the positive electrode paste comprises a lithium-rich manganese-based material and a conductive material, the conductive material comprises carbon nanotubes, and the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotubes is (233-2.6×10 4 ):1. 根据权利要求1所述的正极片，其中，所述富锂锰基材料的中值粒径Dv50与所述碳纳米管的管径之比为(2.6×103～2.4×104):1；The positive electrode sheet according to claim 1, wherein the ratio of the median particle size Dv50 of the lithium-rich manganese-based material to the tube diameter of the carbon nanotube is (2.6×10 3 to 2.4×10 4 ):1; 和/或，所述富锂锰基材料包括多晶结构。And/or, the lithium-rich manganese-based material includes a polycrystalline structure. 根据权利要求1或2所述的正极片，其中，所述碳纳米管的管径为0.5nm～30nm；The positive electrode sheet according to claim 1 or 2, wherein the diameter of the carbon nanotubes is 0.5 nm to 30 nm; 和/或，所述碳纳米管的长度＜30μm。And/or, the length of the carbon nanotube is less than 30 μm. 根据权利要求1-3中任意一项所述的正极片，其中，所述碳纳米管包括单壁碳纳米管和/或多壁碳纳米管；The positive electrode sheet according to any one of claims 1 to 3, wherein the carbon nanotubes include single-walled carbon nanotubes and/or multi-walled carbon nanotubes; 优选地，所述碳纳米管为单壁碳纳米管；Preferably, the carbon nanotubes are single-walled carbon nanotubes; 优选地，所述单壁碳纳米管的管径为0.5nm～3nm，和/或，所述单壁碳纳米管的长度为600nm～8400nm，和/或，所述单壁碳纳米管的长径比为(200～16800):1。Preferably, the diameter of the single-walled carbon nanotube is 0.5 nm to 3 nm, and/or the length of the single-walled carbon nanotube is 600 nm to 8400 nm, and/or the aspect ratio of the single-walled carbon nanotube is (200 to 16800):1. 根据权利要求1-4中任一项所述的正极片，其中，以所述正极涂膏的总重量为基准，所述碳纳米管的重量含量为0.01wt％～3wt％，优选为0.01wt％～0.5wt％。The positive electrode sheet according to any one of claims 1 to 4, wherein the weight content of the carbon nanotubes is 0.01wt% to 3wt%, preferably 0.01wt% to 0.5wt%, based on the total weight of the positive electrode paste. 根据权利要求1-5中任意一项所述的正极片，其中，所述富锂锰基材料的化学式为xLi2MnO3·(1-x)LiMzNyO2，其中，0＜x＜1，0≤y＜1，0≤z＜1；The positive electrode sheet according to any one of claims 1 to 5, wherein the chemical formula of the lithium-rich manganese-based material is xLi 2 MnO 3 ·(1-x)LiM z N y O 2 , wherein 0＜x＜1, 0≤y＜1, 0≤z＜1; M包括Ni、Co和Mn中的一种或多种； M includes one or more of Ni, Co and Mn; N包括Al、Cr、Nb、Mg、Mo、Ta和V中的一种或多种；N includes one or more of Al, Cr, Nb, Mg, Mo, Ta and V; 和/或，所述富锂锰基材料的比表面积为1m2/g～4m2/g，优选为1.5m2/g～3m2/g；and/or, the specific surface area of the lithium-rich manganese-based material is 1 m 2 /g to 4 m 2 /g, preferably 1.5 m 2 /g to 3 m 2 /g; 和/或，所述富锂锰基材料的振实密度为1g/cm3～3g/cm3，优选为1.2g/cm3～2g/cm3。And/or, the tap density of the lithium-rich manganese-based material is 1 g/cm 3 to 3 g/cm 3 , preferably 1.2 g/cm 3 to 2 g/cm 3 . 根据权利要求1-6中任意一项所述的正极片，其中，所述富锂锰基材料的中值粒径Dv50为7μm～13μm，优选为8μm～12μm；The positive electrode sheet according to any one of claims 1 to 6, wherein the median particle size Dv50 of the lithium-rich manganese-based material is 7 μm to 13 μm, preferably 8 μm to 12 μm; 和/或，富锂锰基材料的Dv10为1μm～7μm，优选为3μm～6μm；and/or, the Dv10 of the lithium-rich manganese-based material is 1 μm to 7 μm, preferably 3 μm to 6 μm; 和/或，富锂锰基材料的Dv90为13μm～23μm，优选为15μm～20μm。And/or, the Dv90 of the lithium-rich manganese-based material is 13 μm to 23 μm, preferably 15 μm to 20 μm. 根据权利要求1-7中任意一项所述的正极片，其中，所述导电材料还包括导电剂，所述导电剂包括导电炭黑、碳纤维和石墨烯中的一种或多种；优选地，导电炭黑包含科琴黑、乙炔黑、KS-6、KS-15和S-O中的至少一种；优选地，石墨烯包含SEG-6；The positive electrode sheet according to any one of claims 1 to 7, wherein the conductive material further comprises a conductive agent, and the conductive agent comprises one or more of conductive carbon black, carbon fiber and graphene; preferably, the conductive carbon black comprises at least one of Ketjen black, acetylene black, KS-6, KS-15 and S-O; preferably, the graphene comprises SEG-6; 和/或，以所述正极涂膏的总重量为基准，所述富锂锰基材料的重量含量为90wt％～99.8wt％，所述导电材料的重量含量为0.1wt％～5wt％。And/or, based on the total weight of the positive electrode paste, the weight content of the lithium-rich manganese-based material is 90wt% to 99.8wt%, and the weight content of the conductive material is 0.1wt% to 5wt%. 根据权利要求8所述的正极片，其中，所述碳纳米管的重量与所述导电剂的重量之比为(0.002～1.5):1，优选为(0.002～0.14):1。The positive electrode sheet according to claim 8, wherein the ratio of the weight of the carbon nanotubes to the weight of the conductive agent is (0.002-1.5):1, preferably (0.002-0.14):1. 根据权利要求1-9中任意一项所述的正极片，其中，以所述正极涂膏的总重量为基准，所述富锂锰基材料的重量含量为92wt％～98wt％，所述导电材料的重量含量为1wt％～4wt％。The positive electrode sheet according to any one of claims 1 to 9, wherein, based on the total weight of the positive electrode paste, the weight content of the lithium-rich manganese-based material is 92wt% to 98wt%, and the weight content of the conductive material is 1wt% to 4wt%. 根据权利要求1-10中任意一项所述的正极片，其中，所述正极涂膏包括粘结剂； The positive electrode sheet according to any one of claims 1 to 10, wherein the positive electrode paste comprises a binder; 优选地，所述粘结剂包括聚偏氟乙烯、聚偏氟乙烯－六氟丙烯的共聚物、聚六氟丙烯、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯吡咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯和聚四氟乙烯中的一种或多种。Preferably, the binder includes one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyhexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylic acid salt, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate and polytetrafluoroethylene. 根据权利要求11所述的正极片，其中，以所述正极涂膏的总重量为基准，所述粘结剂的重量含量为0.1wt％～5wt％。The positive electrode sheet according to claim 11, wherein the weight content of the binder is 0.1wt% to 5wt% based on the total weight of the positive electrode paste. 根据权利要求12所述的正极片，其中，所述正极涂膏的总重量为基准，所述粘结剂的重量含量为1wt％～4wt％。The positive electrode sheet according to claim 12, wherein the weight content of the binder is 1wt% to 4wt% based on the total weight of the positive electrode paste. 一种电池，其特征在于，所述电池包括权利要求1-13中任一项所述的正极片。A battery, characterized in that the battery comprises the positive electrode sheet according to any one of claims 1 to 13. 根据权利要求14所述的电池，其中，所述电池为锂离子电池。 The battery according to claim 14, wherein the battery is a lithium ion battery.
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