WO2024036485A1 - Matériau actif d'électrode négative, procédé de fabrication, batterie secondaire et dispositif électrique - Google Patents

Matériau actif d'électrode négative, procédé de fabrication, batterie secondaire et dispositif électrique Download PDF

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WO2024036485A1
WO2024036485A1 PCT/CN2022/112832 CN2022112832W WO2024036485A1 WO 2024036485 A1 WO2024036485 A1 WO 2024036485A1 CN 2022112832 W CN2022112832 W CN 2022112832W WO 2024036485 A1 WO2024036485 A1 WO 2024036485A1
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lithium
graphite
active material
coating layer
negative active
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PCT/CN2022/112832
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English (en)
Chinese (zh)
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俸靖杰
李星
张辰辰
王朴
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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 PCT/CN2022/112832 priority Critical patent/WO2024036485A1/fr
Priority to CN202280088258.4A priority patent/CN118511325A/zh
Publication of WO2024036485A1 publication Critical patent/WO2024036485A1/fr

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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
    • H01M4/36—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
    • H01M4/36—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of lithium batteries, and in particular to a negative active material, a manufacturing method, a secondary battery and an electrical device.
  • lithium-ion batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of lithium-ion batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
  • SEI film solid electrolyte interface film
  • the components of the SEI film are inorganic lithium salts in the inner layer, including Li 2 CO 3 , Li 2 O, and LiF, and organic lithium salts in the outer layer, including lithium alkyl esters.
  • SEI film has a crucial impact on the performance of electrode materials.
  • the formation of the SEI film consumes part of the active lithium, which increases the irreversible capacity of the first charge and discharge and reduces the charge and discharge efficiency of the electrode material; on the other hand, the SEI film is insoluble in organic solvents and can exist stably in organic electrolyte solutions.
  • solvent molecules cannot pass through this passivation film, which can effectively prevent the co-embedding of solvent molecules and avoid the damage to the electrode material caused by the co-embedding of solvent molecules, thus greatly improving the cycle performance and service life of the electrode. Therefore, finding effective ways to improve the performance of SEI membranes has always been a research hotspot in the world's electrochemistry community.
  • This application was made in view of the above issues, and its purpose is to provide a negative active material whose internal pores and particle surfaces are coated with lithium salts, so that the negative active material has higher structural stability, thereby effectively The first Coulombic efficiency and cycle stability of the corresponding battery are greatly improved.
  • a first aspect of the present application provides a negative active material, which includes graphite particles with internal pores and a lithium salt coating layer coating the internal pores of the graphite particles and the outer surface of the particles, wherein the interior of the graphite particles
  • the weight ratio of the lithium element in the pores to the lithium element on the outer surface of the graphite particles is 1 to 10:1.
  • the negative active material of the present application is coated with lithium salt in both its internal pores and particle surface, and reaches a specific weight ratio of lithium element in the internal pores to lithium element on the outer surface of the graphite particles, wherein the coating layer
  • the lithium salt component is part of the SEI film component formed spontaneously in the lithium ion electrochemical system, and the coating layer can inhibit the active sites, thereby reducing the consumption of active lithium during the first formation of the SEI film of the corresponding battery; due to
  • the internal pores of the negative active material are also coated with lithium salt, so that after the internal pores of the graphite are subsequently exposed due to expansion and contraction of the cycle volume, the graphite surface can be protected and the consumption of lithium salt can be further reduced. Therefore, when the negative active material is used as the negative electrode of a lithium-ion battery, it can effectively improve the first Coulombic efficiency and cycle stability of the lithium-ion battery.
  • the lithium salt coating layer meets at least one of the following characteristics:
  • the content of the lithium salt coating layer is 0.01%-6%, based on the total weight of the negative active material
  • the thickness of the lithium salt coating layer in the internal pores of the graphite particles is 1-20 nm, and the thickness of the lithium salt coating layer on the outer surface of the graphite particles is 1-30 nm.
  • the negative active material satisfies at least one of the following characteristics:
  • the graphite is natural graphite
  • the lithium salt is an inorganic lithium salt, optionally one or more selected from the group consisting of carbonate, lithium oxide, lithium phosphate and lithium fluoride.
  • the structural stability of the negative active material is further improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the average volume particle diameter D v50 of the negative active material is 10-30 ⁇ m.
  • the structural stability of the negative active material is further improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the coating amount of the carbon coating layer is 0.2-10%, based on the total amount of the negative active material Weight scale. Therefore, by adding a carbon coating layer between the graphite and lithium salt coating layers, the instability of the surface after the internal pores of the particles are exposed is further suppressed, and the structural stability of the negative electrode active material is improved, thereby effectively improving the corresponding The first Coulombic efficiency and cycle stability of the battery.
  • a second aspect of the application provides a method for preparing a negative active material, which includes:
  • the negative active material includes graphite with internal pores and a lithium salt coating layer covering the internal pores and outer surface of the graphite, wherein the weight ratio of the lithium element in the internal pores of the graphite to the lithium element on the outer surface of the graphite is 1 ⁇ 10:1.
  • the method of the present application successively coats the flake graphite and the shaped spherical graphite to obtain a negative active material in which the internal pores and the outer surface of the graphite are coated with lithium salt, in which the surface of the coated flake graphite is shaped. Finally, the internal pore surface of spherical graphite is formed.
  • the resulting negative active material has higher surface stability, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • carbon coating or surface treatment is performed between steps (1) and (2) or between steps (3) and (4).
  • steps (1) and (2) or between steps (3) and (4) are further suppressed, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • steps (3) and (4) carbon coating or surface treatment is performed.
  • graphite surface defects and activity of active sites are further suppressed, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the lithium-containing raw material includes at least one of lithium carbonate, lithium hydroxide, lithium carboxylate, lithium sulfate, lithium fluoride, and lithium phosphate, optionally Contains at least one of lithium carbonate, lithium acetate, lithium citrate, lithium oxalate, lithium sulfate, lithium fluoride, and lithium phosphate. Therefore, the type of lithium salt in the coating layer is further optimized to improve the surface stability of the negative active material, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • step (2) includes: preparing lithium-containing raw materials into corresponding solutions; dispersing the flake graphite in the solution to obtain a mixture; filtering, drying and dispersing the mixture, A solid powder is obtained; the solid powder is sintered at 300-900°C for 0.5-8 hours under a protective atmosphere or vacuum to form a lithium salt coating layer on the surface of the flake graphite.
  • the quality of the flake graphite surface coating layer is further optimized, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • a third aspect of the present application also provides a secondary battery, characterized in that:
  • the secondary battery thus obtained has improved first Coulombic efficiency and cycle stability.
  • a fourth aspect of the present application provides an electrical device, including a secondary battery selected from the second aspect of the present application.
  • the internal pores and particle surfaces of the negative active material of the present application are coated with lithium salts, so that the negative active material has higher structural stability, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • Figure 1 is an SEM image of a cross-section of natural graphite coated with the negative active material in Example 1 of the present application;
  • Figure 2 is an SEM image of a cross section of existing artificial graphite.
  • FIG. 3 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 4 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 5 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.
  • Secondary battery 51. Housing; 52. Electrode assembly; 53. Cover plate; 6. Electrical device.
  • 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. Furthermore, 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: 1-3, 1-4, 1-5, 2- 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
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • 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).
  • a solid electrolyte interface film (SEI film) will be formed on the surface of the negative electrode during the first charging process.
  • the reaction stops until the SEI film completely covers the surface of the negative electrode.
  • the components of the SEI film are inorganic lithium salts in the inner layer, including Li 2 CO 3 , Li 2 O, and LiF, and organic lithium salts in the outer layer, including lithium alkyl esters.
  • the formation of SEI film has a crucial impact on the performance of electrode materials.
  • the formation of the SEI film consumes part of the active lithium, which increases the irreversible capacity of the first charge and discharge and reduces the charge and discharge efficiency of the electrode material; on the other hand, the SEI film is insoluble in organic solvents and can exist stably in organic electrolyte solutions. Moreover, solvent molecules cannot pass through this passivation film, which can effectively prevent the co-embedding of solvent molecules and avoid the damage to the electrode material caused by the co-embedding of solvent molecules, thus greatly improving the cycle performance and service life of the electrode. Therefore, finding effective ways to improve the performance of SEI membranes has always been a research hotspot in the world's electrochemistry community.
  • the negative active material of the first aspect of the present invention is pre-coated with lithium salts that constitute a part of the SEI film on both its internal pores and particle surfaces, and achieves a specific lithium element in the internal pores and lithium on the outer surface of the graphite particles.
  • the weight ratio of the elements reduces the consumption of active lithium during the first formation of the SEI film of the corresponding battery; since the internal pores of the negative active material are also coated with lithium salts, subsequent internal pores of graphite can be generated due to cycle volume. After being exposed due to expansion and contraction, the graphite surface is protected and further reduces lithium salt consumption. Therefore, when the negative active material is used as the negative electrode of a lithium-ion battery, it can effectively improve the first Coulombic efficiency and cycle stability of the lithium-ion battery.
  • the first aspect of the present application provides a negative active material, which includes graphite particles having internal pores and a lithium salt coating layer coating the internal pores of the graphite particles and the outer surface of the particles, wherein the graphite particles
  • the weight ratio of the lithium element in the internal pores to the lithium element on the outer surface of the graphite particles is 1 to 10:1, preferably 1 to 5:1, and more preferably 2 to 3:1.
  • the negative active material of the present application is coated with lithium salt in both its internal pores and particle surface, and reaches a specific weight ratio of lithium element in the internal pores to lithium element on the outer surface of the graphite particles, wherein the coating layer
  • the lithium salt component is part of the SEI film component formed spontaneously in the lithium ion electrochemical system, and the coating layer can inhibit the active sites, thereby reducing the consumption of active lithium during the first formation of the SEI film of the corresponding battery; due to
  • the internal pores of the negative active material are also coated with lithium salt, so that after the internal pores of the graphite are subsequently exposed due to expansion and contraction of the cycle volume, the graphite surface can be protected and the consumption of lithium salt can be further reduced. Therefore, when the negative active material is used as the negative electrode of a lithium-ion battery, it can effectively improve the first Coulombic efficiency and cycle stability of the lithium-ion battery.
  • the term "internal pores” includes pores or gaps inside graphite particles that are connected or disconnected from the outside air, see Figure 1 .
  • the lithium salt coating layer of the internal pores is obtained by first coating the surface of the flake graphite with lithium salt, and then shaping the lithium salt coating layer on the surface of the flake graphite to form the lithium salt coating layer on the surface of the internal pores of the spherical graphite. get.
  • the content of the lithium salt coating layer is 0.01%-6%, preferably 1%-5.2%, more preferably 2.7-5.15%, based on the total weight of the negative active material.
  • the thickness of the lithium salt coating layer in the internal pores of the graphite particles is 1-20 nm, preferably 2-25 nm, and further preferably 5-12 nm; the thickness of the lithium salt coating layer on the outer surface of the graphite particles is It is 1-30nm, preferably 2-25nm, further preferably 5-12nm.
  • At least 70%, preferably 90%, further preferably 95%, further preferably 98% and most preferably 100% of the surface of the internal pores of the graphite particles are covered by a lithium salt coating layer, based on the interior of the graphite particles. Surface area of all pores.
  • the graphite is natural graphite, and its specific surface area is 2 to 15 m 2 /g.
  • the lithium salt is an inorganic lithium salt, optionally one or more selected from the group consisting of carbonate, lithium oxide, lithium phosphate and lithium fluoride, further optionally selected from the group consisting of lithium carbonate, lithium oxide and fluoride.
  • the inorganic lithium salt is usually preferably a component in the SEI film formed spontaneously in a lithium battery or a component that plays the same role as the SEI film formed spontaneously, that is, it can conduct lithium ions but cannot conduct electrons.
  • the natural graphite has a large specific surface area and many surface active sites, and will consume more active lithium during the first formation of the SEI film.
  • the negative active material of the present application of natural graphite with a lithium salt coating layer on both the internal pores and the external surface is used in a lithium-ion battery, it can not only reduce the consumption of active lithium during the first formation process, but also reduce the subsequent internal pores of the natural graphite due to the After the cycle volume expands and contracts and is exposed, the surface of the natural graphite is protected and the consumption of lithium salt is further reduced; thus, the structural stability of the negative active material is further improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery. sex.
  • the average volume particle diameter D v50 of the negative active material is 10-30 ⁇ m, preferably 14-18 ⁇ m.
  • the average volume particle size Dv50 is the particle size corresponding to when the cumulative volume distribution percentage of the sample reaches 50%; it is measured using a laser particle size analyzer such as the Mastersizer 3000 laser particle size analyzer of Malvern Instruments Co., Ltd. in the UK.
  • the structural stability of the negative active material is further improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the coating amount of the carbon coating layer is 0.2-10%, preferably 0.5-3%, It is further preferably 1.5-2.5%, more preferably 1.78-2.08%, based on the total weight of the negative active material. Therefore, by adding a carbon coating layer between the graphite and lithium salt coating layers, the instability of the surface after the internal pores of the particles are exposed is further suppressed, and the structural stability of the negative electrode active material is improved, thereby effectively improving the corresponding The first Coulombic efficiency and cycle stability of the battery.
  • the coating layer such as a lithium salt coating layer or a carbon coating layer
  • the coating layer is uniformly or patchyly coated on the outer surface of the graphite particles.
  • the area of the coating layer accounts for more than 80% of the surface area of the particles, preferably more than 90%, and further more than 97%.
  • the coating layer can fill the pores, or it can only cover the surface of the pores.
  • a second aspect of the application provides a method for preparing a negative active material, which includes:
  • the negative active material includes graphite with internal pores and a lithium salt coating layer covering the internal pores and outer surface of the graphite, wherein the weight ratio of the lithium element in the internal pores of the graphite to the lithium element on the outer surface of the graphite is 1 ⁇ 10:1.
  • the method of the present application successively coats the flake graphite and the shaped spherical graphite to obtain a negative active material in which the internal pores and the outer surface of the graphite are coated with lithium salt, in which the surface of the coated flake graphite is shaped. Finally, the internal pore surface of spherical graphite is formed.
  • the resulting negative active material has higher surface stability, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the flake graphite is natural flake graphite, its plane size is about 50-200 ⁇ m, measured according to a scanning electron microscope; its fixed carbon content is 99.5%, measured according to a high-frequency infrared carbon and sulfur analyzer .
  • the negative active material includes all technical features described in the first aspect of the invention.
  • carbon coating or surface treatment is performed between steps (1) and (2) or between steps (3) and (4).
  • steps (1) and (2) or between steps (3) and (4) graphite surface defects and activity of active sites are further suppressed, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • steps (3) and (4) carbon coating or surface treatment is performed.
  • graphite surface defects and activity of active sites are further suppressed, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • the step of carbon coating includes mixing (eg stirring) the material to be coated and the carbonaceous material in a heating device such as a heating furnace at a temperature of 150-300°C for 10-60 minutes, and then The obtained mixture is placed in a sintering device and carbonized under an inert gas atmosphere at a temperature of 900-1500°C and a pressure of 0.05-0.2MPa, optionally normal pressure such as 0.1MPa, for 1-10 hours, preferably 4-6 hours, a carbon-coated material was obtained.
  • the carbonaceous material includes one or more of asphalt, phenolic resin, epoxy resin, sucrose, and glucose, preferably asphalt and phenolic resin.
  • the inert gas includes one or more of nitrogen, argon, helium, etc., preferably nitrogen.
  • the surface treatment includes surface oxidation, wherein the surface oxidation includes soaking the powder in strong oxidant solutions such as nitric acid and hydrogen peroxide for oxidation and high-temperature heat treatment in air and oxygen.
  • strong oxidant solutions such as nitric acid and hydrogen peroxide for oxidation and high-temperature heat treatment in air and oxygen.
  • the lithium-containing raw material includes at least one of lithium carbonate, lithium hydroxide, lithium carboxylate, lithium sulfate, lithium fluoride, and lithium phosphate, optionally Contains at least one of lithium carbonate, lithium acetate, lithium citrate, lithium oxalate, lithium sulfate, lithium fluoride, and lithium phosphate, and optionally further contains at least one of lithium carbonate, lithium acetate, lithium citrate, and lithium fluoride. kind. Therefore, the type of lithium salt in the coating layer is further optimized to improve the surface stability of the negative active material, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • step (2) includes: preparing lithium-containing raw materials into corresponding solutions; dispersing the flake graphite in the solution to obtain a mixture; filtering, drying and dispersing the mixture, A solid powder is obtained; the solid powder is sintered at 300-900°C for 0.5-8 hours under a protective atmosphere or vacuum to form a lithium salt coating layer on the surface of the flake graphite.
  • the quality of the flake graphite surface coating layer is further optimized, and the surface stability of the negative active material is improved, thereby effectively improving the first Coulombic efficiency and cycle stability of the corresponding battery.
  • step (2) in the solution of the lithium-containing raw material, the solvent used is water or ethanol; the concentration of the lithium-containing raw material is 10-50% by weight, based on the solution Total weight.
  • the flake graphite is dispersed in the solution by stirring at 500-1200rpm, preferably 600-1000rpm using a stirring and mixing device to obtain a mixture; wherein the weight ratio of flake graphite to lithium-containing raw materials is 1:0.01-0.5 , preferably 1:0.05-0.2.
  • a vacuum filter to filter the mixture at room temperature under a pressure of 0.002-0.05MPa, preferably 0.008-0.012mPa, and dry it in a drying oven at a temperature of 50-150°C, preferably 80-100°C for 3-12 hours, 4 -8 hours, and use an airflow disperser to disperse for 0.5-5 hours, preferably 1-3 hours, to obtain a solid powder; the solid powder is heated at 300-900°C, preferably 400-900°C, under a protective atmosphere or vacuum. Sintering for 0.5-8h, preferably 0.5-5h, forms a lithium salt coating layer on the surface of the flake graphite, and then naturally cools to room temperature.
  • the lithium salt contains The composition of the coating is usually lithium carbonate; when the solid powder is sintered at 750-900°C for 0.5-3h, the lithium salt coating is usually composed of lithium carbonate and lithium oxide. When the sintering temperature is high or long enough, the lithium salt coating may even end up consisting solely of lithium oxide.
  • step (3) the flake graphite obtained in step (2) is shaped to obtain spherical graphite with an average volume particle diameter Dv50 of 5-40 ⁇ m, wherein the average volume particle diameter Dv50 is measured as above narrate.
  • step (3) includes sequentially crushing and shaping the flake graphite obtained in step (2) in an airflow crushing and shaping machine, and dispersing in an airflow dispersing machine for 0.5-5 hours, preferably 1-3 hours, Sieve in a vibrating screening machine to obtain spherical graphite particles with an average volume particle size Dv50 of 5-40 ⁇ m.
  • the surface of the coated flake graphite forms the surface of the internal pores of the spherical particles, and further, the surface lithium salt coating layer of the flake graphite also forms the surface coating of the internal pores of the spherical particles. Cladding. It should be noted that it is not excluded that the surface lithium salt coating layer of the flake graphite will also form a coating layer on a part of the external surface of the spherical particles, and this part of the external surface area of the spherical particles does not account for more than 40% of the surface area of the particles.
  • the spherical graphite is coated with a lithium-containing raw material so that a lithium salt coating layer is formed on the surface of the spherical graphite to obtain the negative active material.
  • lithium-containing raw materials are prepared into corresponding solutions; the spherical graphite is dispersed in the solution to obtain a mixture; the mixture is filtered, dried and dispersed to obtain solid powder; the solid is The powder is sintered at 300-900°C for 0.5-8 hours under a protective atmosphere or vacuum to form a lithium salt coating layer on the surface of the spherical graphite.
  • the lithium-containing raw materials described in step (4) are as described in step (2), and may be the same as or different from those described in step (4). Other technical features required in step (4) are as described in step (2).
  • a third aspect of the present application also provides a secondary battery, characterized in that:
  • the secondary battery thus obtained has improved first Coulombic efficiency and cycle stability.
  • a fourth aspect of the present application provides an electrical device, including a secondary battery selected from the second aspect of the present application.
  • a secondary battery is provided.
  • a secondary battery typically includes a positive electrode plate, a negative 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 opposite 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 a metal material on a polymer material substrate.
  • metal materials include but are not limited to aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.
  • Polymer material substrates such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) ) etc.
  • the cathode active material may include cathode active materials 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 oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the weight ratio of the positive electrode active material in the positive electrode film layer is 80-100% by weight, based on the total weight of the positive electrode film layer count.
  • 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 weight ratio of the binder in the positive electrode film layer is 0-20% by weight, based on the total weight of the positive electrode film layer.
  • 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 weight ratio of the conductive agent in the positive electrode film layer is 0-20% by weight, based on the total weight of the positive electrode film layer.
  • 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), forming a positive electrode slurry, wherein the solid content of the positive electrode slurry is 40-80wt%, the viscosity at room temperature is adjusted to 5000-25000mPa ⁇ s, and the positive electrode slurry is coated on the surface of the positive electrode current collector , dried and cold-pressed by a cold rolling mill to form a positive electrode piece; the unit area density of the positive electrode powder coating is 150-350 mg/m 2 , and the compacted density of the positive electrode piece is 3.0-3.6g/cm 3 , optionally 3.3 -3.5g/cm 3 .
  • the calculation formula of the compacted density is
  • Compaction density coating surface density / (thickness of electrode piece after extrusion - thickness of current collector).
  • 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.
  • the negative electrode film layer includes the negative electrode active material prepared according to the first aspect of the present invention or according to the second aspect of the present invention.
  • 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 metal foil copper 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 material.
  • the composite current collector can be formed by forming a metal material on a polymer material substrate.
  • metal materials include but are not limited to copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.
  • polymer material substrates include but are not limited to polypropylene (PP), polyethylene terephthalate Glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and other base materials.
  • the weight ratio of the negative active material in the negative electrode film layer is 70-100% by weight, based on the total weight of the negative electrode film layer.
  • 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).
  • SBR styrene-butadiene rubber
  • PAA polyacrylic acid
  • PAAS polysodium acrylate
  • PAM polyacrylamide
  • PVA polyvinyl alcohol
  • SA sodium alginate
  • PMAA methacrylic acid
  • CMCS carboxymethyl chitosan
  • 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 weight ratio of the conductive agent in the negative electrode film layer is 0-20% by weight, based on the total weight of the negative electrode film layer.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • the weight ratio of the other additives in the negative electrode film layer is 0-15% by weight, based on the total weight of the negative electrode film layer.
  • 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), forming a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity at room temperature is adjusted to 2000-10000mPa ⁇ s; the obtained negative electrode slurry is coated on the negative electrode current collector, After the drying process and cold pressing, such as against rollers, the negative electrode piece is obtained.
  • the negative electrode powder coating unit area density is 75-220mg/m 2
  • the negative electrode plate compacted density is 1.2-2.0g/m 3 .
  • 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 and solvents.
  • the electrolyte salt may be selected from lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), bisfluorosulfonyl Lithium amine (LiFSI), lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoromethanesulfonate borate (LiDFOB), lithium difluoromethane borate (LiBOB), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorodioxalate phosphate (LiDFOP) and lithium tetrafluorooxalate phosphate (LiTFOP).
  • the concentration of the electrolyte salt is usually 0.5-5mol/L.
  • the solvent may be selected from fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) ), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), methyl formate (MF), methyl acetate Ester (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB) , one or more of ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS) and diethyl
  • FEC
  • the electrolyte optionally further includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the secondary battery further includes a separator film.
  • a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the thickness of the isolation film is 6-40 ⁇ m, optionally 12-20 ⁇ m; the porosity is 30-60%, and the pore diameter is 100 nm-1.0 ⁇ m.
  • 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. 3 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.
  • 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.
  • a fourth aspect of the present application provides an electrical device, including a secondary battery, a battery module or a battery pack selected from the second aspect of 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.
  • FIG. 5 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.
  • step (2) Add 10kg of 3wt% lithium acetate aqueous solution to the equipment in step (1) and stir at 1200rpm for 5 hours to completely disperse the flake natural graphite. Then use a vacuum filter to filter under a pressure of 0.01 mPa, dry the filtrate in a drying oven at a temperature of 90°C for 6 hours, and then use an airflow disperser to disperse the obtained solid for 2 hours. Finally, the solid was put into a tube furnace, sintered under nitrogen at 450°C for 5 hours at normal pressure, and then naturally cooled to room temperature to obtain Li 2 CO 3 -coated flake natural graphite.
  • step (3) The Li 2 CO 3- coated flake natural graphite obtained in step (2) is sequentially crushed and shaped in an airflow crushing and shaping machine, dispersed in an airflow dispersing machine for 2 hours, and screened in a vibrating screening machine. points to obtain spherical graphite particles with a Dv50 of 20 ⁇ m.
  • the average volume particle size Dv50 of the negative active material is 17 ⁇ m; its SEM image is shown in Figure 1.
  • Other relevant product parameters are summarized in Table 1.
  • step (2) the amount of lithium acetate solution is 10kg of 8wt% lithium acetate aqueous solution, and in step (4), the amount of lithium acetate solution is 10kg of 1wt% of lithium acetate aqueous solution.
  • step (2) the amount of lithium acetate solution is 10kg of 1wt% lithium acetate aqueous solution
  • the amount of lithium acetate solution is 10kg of 8wt% of lithium acetate aqueous solution.
  • step (3i) surface treatment is performed: soak the spherical graphite particles in 80% hydrogen peroxide aqueous solution for 3 hours, then filter, and then sinter. The furnace was maintained at a temperature of 400°C for 1 hour under an oxygen atmosphere, and then cooled naturally.
  • the lithium content in the negative active material particles can be measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • ICP inductively coupled plasma atomic emission spectrometry
  • the concentrated nitric acid is used as a digestion reagent.
  • the graphene and the internal lithium salt can be completely dissolved using the microwave digestion method.
  • the lithium content obtained by the ICP test is the lithium content in the internal pores.
  • the lithium element content within Li is also obtained at the same time as the total carbon content; from this, the weight ratio of the lithium element in the internal pores of the graphite particles to the lithium element on
  • the negative active material of Preparation Example 1, thickener sodium carboxymethylcellulose, adhesive styrene-butadiene rubber, and conductive agent carbon black were mixed according to a mass ratio of 96:1:1:2, and deionized water was added.
  • the organic solvent is a mixed solution containing ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC), where the volume ratio of EC, EMC and DEC is 20:20:60.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the concentration of lithium salt is 1mol/L.
  • Stack the positive electrode sheet, isolation film, and negative electrode sheet in order so that the isolation film plays an isolation role between the positive and negative electrode sheets then roll it into a square bare cell, put it into the aluminum-plastic film, and then heat it at 80 After baking at °C to remove water, 10g of the corresponding non-aqueous electrolyte is injected, sealed, and after standing, hot and cold pressing, formation, clamping, volume separation and other processes, a finished battery with a capacity of 4000mAh is obtained.
  • the secondary battery of Examples 2-11 and the secondary battery of Comparative Example 1 are similar to the secondary battery of Example 1, but use the negative active material of the corresponding preparation example.
  • 1C current constant current charging to 3.65V continue constant voltage charging until the charging current is less than 0.05C and then cut off, record the charging capacity C11; pause for 5 minutes; 1C current constant current discharge to 2.5V, record the discharge capacity C12; pause for 5 minutes.
  • the above is the first charge and discharge cycle of the battery, which is repeated until the battery has cycled 300 times, and the discharge capacity C3002 is recorded.
  • the negative active material of the present application can effectively improve the first Coulombic efficiency and cycle stability of the corresponding battery; for example, the first Coulombic efficiency of the corresponding secondary battery can reach more than 89%, 300 The capacity retention rate after lap can reach more than 95%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau actif d'électrode négative, qui comprend des particules de graphite ayant des pores internes et une couche de revêtement de sel de lithium revêtant les pores internes des particules de graphite et des surfaces externes de particules, le rapport en poids d'un élément lithium dans les pores internes des particules de graphite à un élément lithium sur les surfaces externes de particules de graphite étant de 1 à 10 : 1. La présente invention concerne un procédé de fabrication du matériau actif d'électrode négative, une batterie secondaire correspondante et un dispositif électrique. Les pores internes et les surfaces de particules du matériau actif d'électrode négative sont tous revêtus de sels de lithium, de telle sorte que le matériau actif d'électrode négative présente une stabilité structurale supérieure, ce qui permet d'améliorer efficacement le premier rendement coulombien et la stabilité de cyclage de la batterie correspondante.
PCT/CN2022/112832 2022-08-16 2022-08-16 Matériau actif d'électrode négative, procédé de fabrication, batterie secondaire et dispositif électrique WO2024036485A1 (fr)

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CN202280088258.4A CN118511325A (zh) 2022-08-16 2022-08-16 负极活性材料、制法、二次电池和用电装置

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004063321A (ja) * 2002-07-30 2004-02-26 Jfe Chemical Corp 複合黒鉛質粒子およびその製造方法ならびにリチウムイオン二次電池用負極およびリチウムイオン二次電池
JP2008186732A (ja) * 2007-01-30 2008-08-14 Nippon Carbon Co Ltd リチウム二次電池用負極活物質、それを使用した負極及び製造方法
EP2913299A1 (fr) * 2014-02-27 2015-09-02 Kangwon National University University Industry Coorporation Matériau actif négatif pour batterie au lithium rechargeable, procédé de préparation de celui-ci, et batterie au lithium rechargeable comprenant celui-ci
US20200044240A1 (en) * 2016-10-07 2020-02-06 Kratos LLC Graphite and Group IVA Composite Particles and Methods of Making
CN113644241A (zh) * 2021-07-15 2021-11-12 恒大新能源技术(深圳)有限公司 复合石墨负极材料及其制备方法、二次电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004063321A (ja) * 2002-07-30 2004-02-26 Jfe Chemical Corp 複合黒鉛質粒子およびその製造方法ならびにリチウムイオン二次電池用負極およびリチウムイオン二次電池
JP2008186732A (ja) * 2007-01-30 2008-08-14 Nippon Carbon Co Ltd リチウム二次電池用負極活物質、それを使用した負極及び製造方法
EP2913299A1 (fr) * 2014-02-27 2015-09-02 Kangwon National University University Industry Coorporation Matériau actif négatif pour batterie au lithium rechargeable, procédé de préparation de celui-ci, et batterie au lithium rechargeable comprenant celui-ci
US20200044240A1 (en) * 2016-10-07 2020-02-06 Kratos LLC Graphite and Group IVA Composite Particles and Methods of Making
CN113644241A (zh) * 2021-07-15 2021-11-12 恒大新能源技术(深圳)有限公司 复合石墨负极材料及其制备方法、二次电池

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