WO2023208058A1 - Feuille d'électrode négative, son procédé de préparation, batterie et procédé de préparation de matériau d'électrode négative - Google Patents

Feuille d'électrode négative, son procédé de préparation, batterie et procédé de préparation de matériau d'électrode négative Download PDF

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WO2023208058A1
WO2023208058A1 PCT/CN2023/090928 CN2023090928W WO2023208058A1 WO 2023208058 A1 WO2023208058 A1 WO 2023208058A1 CN 2023090928 W CN2023090928 W CN 2023090928W WO 2023208058 A1 WO2023208058 A1 WO 2023208058A1
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negative electrode
silicon
carbon
active material
tin
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PCT/CN2023/090928
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English (en)
Chinese (zh)
Inventor
金周
黄学杰
王丕涛
胡保平
闫勇
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松山湖材料实验室
中国科学院物理研究所
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Publication of WO2023208058A1 publication Critical patent/WO2023208058A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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 application relates to the technical field of secondary batteries, and in particular to a negative electrode plate and a preparation method thereof, a battery, and a preparation method of negative electrode materials.
  • lithium-ion batteries Due to the rapid development and widespread application of portable electronic devices and electric vehicles, there is an urgent need for lithium-ion batteries with high specific energy and long cycle life.
  • commercialized lithium-ion batteries mainly use graphite as the negative electrode material.
  • the theoretical specific capacity of graphite is only 372mAh/g, which limits the further improvement of the specific energy of lithium-ion batteries.
  • the theoretical specific capacity of silicon can reach up to 4200mAh/g. However, the volume of silicon expands by more than 300% during the lithium storage process, resulting in a decrease in performance.
  • the purpose of the embodiments of the present application includes providing a negative electrode plate and a preparation method thereof, a battery, and a preparation method of negative electrode materials, so as to reduce the impact of the expansion of the sheet-like silicon-based material on battery performance.
  • embodiments of the present application provide a negative electrode sheet, including a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector.
  • the active material in the negative active material layer includes sheet-shaped silicon-based material, and based on the surface of the negative electrode current collector, at least 60% of the sheet-shaped silicon-based material has an angle of ⁇ 20° with the surface of the negative electrode current collector.
  • the angle between at least 60% of the sheet-shaped silicon-based material and the surface of the negative electrode current collector is ⁇ 20°.
  • the sheet-shaped silicon-based material tends to be parallel to the negative electrode current collector, and along the thickness direction of the negative electrode plate, the sheet-shaped silicon-based material tends to Arranged in parallel and forming a stacked structure, the structure can be made more stable; during the charging and discharging process, the volume of the sheet-like silicon-based material changes and slides along the thickness direction, which can fill the gaps inside the negative electrode plate, making the electrode plate have good of electrical contact and integrity, the battery performs better.
  • the sheet-like silicon-based materials are silicon nanosheets, silicon submicron sheets, silicon alloy nanosheets, silicon alloy submicron sheets, silicon-oxygen nanosheets, silicon-oxygen submicron sheets and their surface modifications One or more materials after coating.
  • the silicon nanosheet has a thickness of 1-200 nm and a planar size of 20-5000 nm.
  • the active material may also include carbon-coated tin nanowires as a synergistic active material.
  • the diameter of the carbon-coated tin nanowire is below 100 nm, and the aspect ratio is (5-1000):1.
  • carbon-coated tin nanowires are formed by in-situ reduction of tin oxide nanoparticles and carbon deposition.
  • the active material further includes carbon nanotubes as synergistic active materials.
  • the diameter of the carbon nanotube is less than 20 nm, and the aspect ratio is (10-1000):1.
  • the carbon nanotubes include at least single-walled carbon nanotubes.
  • the sum of the masses of active material, conductive agent and binder is the total mass, the mass of active material accounts for 70%-95% of the total mass, and the mass of conductive agent accounts for 70%-95% of the total mass. It is 0%-10%, and the binder mass accounts for 2%-30% of the total mass.
  • the weight percentage of silicon is 70%-98%
  • the weight percentage of tin is 0.5%-20%
  • the weight percentage of carbon is 1.5-20%.
  • embodiments of the present application provide a lithium ion secondary battery, including the above-mentioned negative electrode plate.
  • embodiments of the present application provide a solid-state battery, including the above-mentioned negative electrode plate.
  • embodiments of the present application provide a method for preparing an anode material, which includes: dispersing a carbon nanotube solution, a silicon-based material, and tin oxide nanoparticles in an organic solvent, grinding, filtering, and drying to obtain a composite precursor.
  • the composite precursor is placed in a high-temperature sintering furnace, heated to 650-900°C in an inert atmosphere, and then acetylene gas is introduced for sintering to obtain a mixture of carbon nanotubes, carbon-coated tin nanowires and sheet-like silicon-based materials. negative electrode material.
  • this application provides a method for preparing a negative electrode sheet, which includes mixing sheet silicon-based materials, conductive agents, binders and solvents in a stirring tank, and then using a stirrer in the stirring tank at 200-3000rad. /min, and the mixing tank itself is continuously rotated at a speed of 200-3000rad/min to obtain the negative active slurry. Then, the negative electrode active slurry is coated on the surface of the negative electrode current collector, dried, and rolled to obtain a negative electrode piece.
  • the angle between at least 60% of the sheet-shaped silicon-based material and the surface of the negative electrode current collector can be ⁇ 20°.
  • the sheet-shaped silicon-based materials tend to be parallel to the negative electrode current collector, and along the thickness direction of the negative electrode sheet, the sheet-shaped silicon-based materials tend to be arranged in parallel and form a stacked structure, which can make the structure more stable; during the charging and discharging process, the sheets
  • the volume change and sliding of the silicon-like material along the thickness direction can fill the gaps inside the negative electrode piece, so that the electrode piece has good electrical contact and integrity, and the battery performance is better.
  • Figure 1 is a scanning electron microscope (SEM) image of the negative electrode piece (original electrode piece) provided in Example 1 of the present application;
  • Figure 2 is a scanning electron microscope (SEM) image of the negative electrode plate (in the fifth cycle of lithium insertion state) provided in Example 1 of the present application;
  • Figure 3 is a scanning electron microscope (SEM) image of the negative electrode piece (original electrode piece) provided in Comparative Example 1;
  • Figure 4 is a scanning electron microscope (SEM) image of the negative electrode plate (in the fifth week of lithium insertion state) provided in Comparative Example 1;
  • Figure 5 is an X-ray diffraction (XRD) pattern of the active material provided in Example 1 of the present application;
  • Figure 6 is an X-ray diffraction (XRD) pattern of the negative electrode plate provided in Example 1 of the present application before rolling;
  • Figure 7 is an X-ray diffraction (XRD) pattern of the negative electrode plate provided in Example 1 of the present application after rolling;
  • Figure 8 is a charge-discharge curve of the half-cell provided in Embodiment 1 of the present application.
  • Figure 9 is a scanning electron microscope (SEM) image of the negative active material provided in Example 1 of the present application.
  • Figure 10 is a scanning electron microscope (SEM) image of the negative active material provided in Example 9 of the present application.
  • Figure 11 is a scanning electron microscope (SEM) image of the negative active material of the battery provided in Example 1 of the present application after 5 weeks of cycling;
  • Figure 12 is a scanning electron microscope (SEM) image of the negative active material provided in Comparative Example 3;
  • Figure 13 is a transmission electron microscope (TEM) image of the carbon-coated tin nanowire provided in Example 1 of the present application;
  • Figure 14 is a transmission electron microscope (TEM) image of the carbon-coated tin nanowire provided in Example 10 of the present application;
  • Figure 15 is an impedance diagram of the battery provided in Example 1 and Example 9 of the present application.
  • Figure 16 is a cycle performance diagram of the battery provided in Example 1 of the present application under 2C conditions.
  • Embodiments of the present application provide a negative electrode sheet, which includes a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector.
  • the negative active material layer includes active material, conductive agent and binder.
  • the sum of the masses of the active material, conductive agent and binder is the total mass, the mass of the active material accounts for 70%-95% of the total mass, and the mass of the conductive agent accounts for 0%-10% of the total mass. %, the binder mass accounts for 5%-30% of the total mass.
  • the density, specific capacity and first charge of the negative active material layer can be improved.
  • the mass percentage of the active material to the total mass is 70%, 75%, 80%, 85%, 90% or 95%; the mass percentage of the conductive agent to the total mass is 0%, 2%, 4%, 6%, 8% or 10%; the percentage of binder mass to the total mass is 2%, 10%, 15%, 20%, 25% or 30%.
  • the conductive agent can be one or more combinations of conductive carbon black, conductive graphite, conductive carbon fiber, carbon nanotubes and graphene;
  • the binder can be carboxymethylcellulose, styrene-butadiene rubber, polyacrylic acid, polyacrylic acid One or a combination of sodium, lithium polyacrylate, sodium alginate, and polyvinylidene fluoride.
  • the active material includes sheet-shaped silicon-based material.
  • Sheet-like silicon-based materials refer to silicon-based materials that contain silicon and can deintercalate lithium; the silicon-based materials are in the form of sheets, and the thickness of the sheet-like materials is at the nanometer level.
  • the flaky silicon-based material is silicon nanosheets (silicon elemental substance), silicon submicron flakes (silicon elemental substance), silicon alloy nanosheets (silicon alloy), silicon alloy submicron flakes (silicon alloy), silicon oxygen nanosheets (Silicon-oxygen material SO x , 0 ⁇ x ⁇ 2) and silicon-oxygen submicron sheets (silica-oxygen material SO x , 0 ⁇ x ⁇ 2) and one or more of their surface-modified and coated materials.
  • silicon nanosheets refer to: silicon element is in the form of a sheet, and the thickness of the silicon sheet is at the nanometer level.
  • the silicon nanosheet has a thickness of 1-100nm and a planar size of 20-5000nm.
  • the thickness of the silicon nanosheet refers to: the maximum distance between the two surfaces of the silicon nanosheet; the plane size of the silicon nanosheet refers to: in the outline of the projection of the sheet-like structure of the silicon nanosheet on the horizontal plane, The distance between the two furthest points.
  • the thickness of silicon nanosheets is 1nm, 5nm, 10nm, 20nm, 40nm, 60nm, 80nm or 100nm;
  • the plane size of silicon nanosheets is 20nm, 50nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200nm, 1400nm , 1600nm, 1800nm or 2000nm.
  • the surface of the silicon nanosheet is also coated with a carbon layer with a thickness of nanometer level.
  • the thin carbon layer can maintain a high specific capacity of the active material; on the other hand, the coating of the carbon layer can avoid direct contact between the flaky silicon-based material and the electrolyte to a certain extent, and the active material The cycle stability of the material is further improved.
  • the thickness of the carbon coating layer on the sheet-shaped silicon-based material is 2-10 nm.
  • the angle between at least 60% of the sheet-shaped silicon-based materials and the surface of the negative electrode current collector is ⁇ 20°; that is, based on the plane direction of the negative electrode current collector, at least The tilt angle between 60% of the sheet silicon-based material and the negative electrode current collector is ⁇ 20°.
  • the sheet-shaped silicon-based materials tend to be parallel to the negative electrode current collector, and along the thickness direction of the negative electrode sheet, the sheet-shaped silicon-based materials tend to be arranged in parallel and form a stacked structure, which can make the structure more stable; during the charging and discharging process, the sheets
  • the volume change and sliding of the silicon-like material along the thickness direction can fill the gaps inside the negative electrode piece, so that the electrode piece has good electrical contact and integrity, and the battery performance is better.
  • the angle between two adjacent pieces of silicon-based material is ⁇ 10°.
  • the distribution of sheet-like silicon-based materials on the negative electrode current collector can be made more consistent, so that more sheet-like silicon-based materials can exist in a stacked form to improve battery performance.
  • the angle between at least 90% of the sheet-like silicon-based materials and the surface of the negative electrode current collector is ⁇ 20°; and along the thickness direction of the negative electrode plate, the angle between two adjacent pieces of sheet-like silicon-based materials is ⁇ 5 °. More sheet-like silicon-based materials are basically parallel to the negative electrode current collector and form a stacked structure, which can make the battery perform better.
  • the angle between all the sheet-shaped silicon-based materials and the surface of the negative electrode current collector is ⁇ 20°. All flaky silicon-based materials basically tend to be parallel to the negative current collector, resulting in better battery performance.
  • the active material also includes carbon-coated tin nanowires as synergistic active materials.
  • Carbon-coated tin nanowires refer to: the surface of the tin nanowires is coated with a carbon layer, and the carbon-coated tin nanowires formed are still linear structures, and their sizes are also nanoscale.
  • the tin material itself has good electrical conductivity and ionic conductivity. When combined with the coating carbon layer, it has rapid charge and discharge capabilities; and the coating of the carbon layer can keep its structure intact during the charge and discharge process and achieve good performance. electrical contact.
  • the thickness of the carbon coating layer in the carbon-coated tin nanowire is nanoscale.
  • the thickness of the carbon coating layer on the carbon-coated tin nanowire is 2-10 nm.
  • the diameter of the carbon-coated tin nanowire is below 100nm, and the aspect ratio is (5-1000):1.
  • the diameters of different parts of the carbon-coated tin nanowires can be the same or different.
  • the diameter is below 100nm and the aspect ratio is (5-1000):1, which can make it more flexible.
  • After mixing the flaky silicon-based materials can form a three-dimensional network structure with flaky silicon-based materials, which can avoid the volume expansion of flaky silicon-based materials to a certain extent.
  • the aspect ratio of the carbon-coated tin nanowire is 5:1, 10:1, 20:1, 40:1, 80:1, 160:1, 320:1, 480:1, 600:1 Or 1000:1.
  • carbon-coated tin nanowires are formed by in-situ reduction of tin oxide nanoparticles and carbon deposition.
  • reducing gas for example, acetylene gas
  • tin oxide is reduced to tin while using tin as a catalyst to obtain carbon-coated tin nanowires with a carbon layer evenly deposited on the surface of the tin nanowires, and the tin nanowires are
  • the carbon layer is uniformly deposited on the surface of the wire, and the carbon layer is more closely combined with the tin nanowire.
  • the carbon layer has a high degree of graphitization, which is beneficial to improving the performance of the negative electrode material.
  • reducing gas for example, acetylene gas
  • tin oxide is reduced to tin while using tin as a catalyst to obtain carbon-coated tin nanowires with a carbon layer evenly deposited on the surface of the tin nanowires, and the tin nanowires are The carbon layer is uniformly deposited on the surface of the wire, and the carbon layer is more closely combined with the tin nanowire.
  • the graphitization degree of the carbon layer is high, which can make the graphitization degree of the carbon layer in the carbon-coated tin nanowire be between 0.3-1. , its graphitization degree is high, which is beneficial to improving the performance of negative electrode materials.
  • the graphitization degree ⁇ of the carbon coating layer in the carbon-coated tin nanowire is 0.3-0.6 or 0.6-1; as an example, the graphitization degree ⁇ of the carbon coating layer in the carbon-coated tin nanowire is is 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.
  • the active material also includes carbon nanotubes as synergistic active materials.
  • Carbon nanotubes refer to carbon materials that are in the form of tubes, and the outer diameter of the carbon tubes is nanoscale.
  • the diameter of carbon nanotubes is below 20nm, and the aspect ratio is (10-1000):1.
  • the diameters of different parts of carbon nanotubes can be similar The same or different, the diameter is below 20nm and the aspect ratio is (10-1000):1. Since both carbon-coated tin nanowires and carbon nanotubes have a certain degree of elasticity and flexibility, when mixed with sheet-like silicon-based materials, a better three-dimensional conductive network can be formed, which can alleviate the volume effect of lithium deintercalation in the negative electrode. , making the battery have a larger specific capacity and higher cycle stability; at the same time, the negative electrode plate has good ionic conductivity and electronic conductivity, and better conductivity.
  • the carbon nanotubes include at least single-walled carbon nanotubes. It can make the performance of the negative electrode piece better.
  • the carbon nanotubes may also be a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes.
  • the weight percentage of silicon is 70%-98%, the weight percentage of tin is 0.5%-20%, and the weight percentage of carbon is 1.5-20%.
  • the weight percentage of silicon, tin and carbon refers to the element content.
  • the weight percentage of carbon refers to the sum of the weight percentage of carbon in carbon-coated tin nanowires and carbon in carbon nanotubes;
  • the weight percentage of silicon refers to the weight percentage of silicon in the sheet-shaped silicon-based material;
  • the weight percentage of tin refers to the weight percentage of tin in the carbon-coated tin nanowires.
  • the weight percentage of silicon is 70%, 74%, 78%, 82%, 86%, 90%, 94% or 98%; the weight percentage of tin is 0.5%, 1%, 2%, 4 %, 8%, 12%, 16% or 20%; carbon weight percentage is 1.5%, 3%, 5%, 8%, 10%, 12%, 14%, 16%, 18% or 20% .
  • the single-surface density of the negative electrode piece provided by this application is 1-40 mg/cm 2 . It can be used to prepare secondary batteries, such as lithium-ion batteries or all-solid-state batteries. It can make the battery have a specific capacity of 1000-3000mAh/g and a first charge and discharge Coulombic efficiency of ⁇ 80% to improve battery performance.
  • the negative active material including flake silicon-based material
  • conductive agent including flake silicon-based material
  • binder and solvent
  • the stirrer in the stirring tank operates at a speed of 200-3000rad/min.
  • the mixing tank itself continuously rotates at a speed of 200-3000rad/min to obtain the negative electrode active slurry.
  • the negative electrode active slurry is coated on the surface of the negative electrode current collector, dried, and rolled to obtain a negative electrode piece.
  • the angle between at least 60% of the sheet-shaped silicon-based material and the surface of the negative electrode current collector can be ⁇ 20°.
  • the sheet-shaped silicon-based materials tend to be parallel to the negative electrode current collector, and along the thickness direction of the negative electrode sheet, the sheet-shaped silicon-based materials tend to be arranged in parallel and form a stacked structure, which can make the structure more stable; during the charging and discharging process, the sheets
  • the volume change and sliding of the silicon-like material along the thickness direction can fill the gaps inside the negative electrode piece, so that the electrode piece has good electrical contact and integrity, and the battery performance is better.
  • the rotation speed of the agitator can be 200-1000rad/min or 1000-3000rad/min
  • the rotation speed of the mixing tank itself can be 200-1000rad/min or 1000-3000rad/min.
  • the rotation speed of the stirrer and the stirring tank can be independently selected from 200rad/min, 500rad/min, 1000rad/min, 1500rad/min, 2000rad/min, 2500rad/min or 3000rad/min.
  • the preparation method of the negative active material can be: dispersing the carbon nanotube solution, silicon-based material, and tin oxide nanoparticles in an organic solvent, grinding (such as ball milling, sand milling, etc.), filtering, and drying to obtain a composite precursor.
  • the composite precursor is placed in a high-temperature sintering furnace, heated to 650-900°C in an inert atmosphere, and then acetylene gas is introduced for sintering to obtain a mixture of carbon nanotubes, carbon-coated tin nanowires and sheet-like silicon-based materials. negative electrode material.
  • the preparation method of the negative active material can also be: put the tin oxide nanoparticles into a high-temperature sintering furnace, raise the temperature to 650-900°C in an inert atmosphere, and introduce acetylene gas for sintering. After sintering, carbon-coated tin can be obtained Nanowires.
  • the carbon nanotube solution, flaky silicon-based material, and carbon-coated tin nanowires are dispersed in an organic solvent, filtered, and dried to obtain a negative electrode material mixed with carbon nanotubes, carbon-coated tin nanowires, and flaky silicon-based materials.
  • tin oxide can be reduced to tin, and at the same time, tin can be used as a catalyst for the deposition of acetylene gas, which can uniformly deposit a carbon layer on the surface of the tin nanowires, and the carbon layer and the tin The nanowires are more tightly bonded, and the carbon layer has a high degree of graphitization in carbon-coated tin nanowires.
  • Carbon nanotubes, carbon-coated tin nanowires, and flaky silicon-based materials are mixed in a solvent to obtain a uniformly mixed anode material; at the same time, the three form a three-dimensional network structure to a certain extent, making the anode material have a higher Good ionic conductivity and electronic conductivity make the negative electrode material perform better.
  • the sintering temperature may be 650-750°C or 750-900°C; as an example, the sintering temperature may be 650°C, 700°C, 750°C, 800°C, 850°C or 900°C.
  • the carbon nanotubes are dispersed in an ethanol solvent to obtain a carbon nanotube solution, where the mass ratio of the carbon nanotubes to ethanol is 1:100.
  • the active material includes silicon nanosheets, carbon-coated tin nanowires and carbon nanotubes, and the surface of the silicon nanosheets is coated with a carbon layer.
  • the thickness of silicon nanosheets is 10-80nm, and the planar size is 200-800nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10- 20nm, aspect ratio is (100-200):1.
  • silicon accounts for 86.6wt% of the active material; tin accounts for 4.6wt% of the active material; carbon accounts for 5.2wt% of the active material; and other substances account for 3.1wt% of the active material.
  • the agitator in the mixing tank continuously stirs at a speed of 500 rad/min, and the mixing tank itself continuously rotates at a speed of 500 rad/min to obtain the negative active material slurry.
  • the negative active material slurry is coated on the surface of the copper foil with a scraper, and then dried to obtain a negative electrode piece.
  • the negative electrode piece is rolled, and a punch is used to prepare a small round piece with a diameter of 15 mm from the rolled negative electrode piece.
  • the above-mentioned negative electrode sheet and lithium sheet are paired and assembled into a button half battery.
  • the battery assembly process is carried out in a glove box filled with argon gas.
  • Celgard2300 membrane is used as the isolation membrane, and the electrolyte is a solution of 1 mol/L LiPF 6 dissolved in EC:DMC:FEC (volume ratio 4.8:4.8:0.4).
  • Example 2 The difference between Example 2 and Example 1 is that in step (2), the solar silicon wafer cutting waste is replaced with silicon oxide with a particle size of 5-10 ⁇ m.
  • the active material includes silicon oxide nanosheets, carbon-coated tin nanowires and carbon nanotubes, and the surface of the silicon oxide nanosheets is coated with a carbon layer.
  • the thickness of silicon oxide nanosheets is 50-80nm, and the planar size is 200-800nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500): 1; the diameter of carbon nanotubes is 10-20nm, aspect ratio is (100-200):1.
  • silicon accounts for 60.8wt% of active materials; oxygen accounts for 29.3wt% of active materials; tin accounts for 4.6wt% of active materials; carbon accounts for 4.8wt% of active materials; other substances account for 0.5% of active materials. wt%.
  • Example 3 The difference between Example 3 and Example 1 is that in step (2), the solar silicon wafer cutting waste is replaced with ferrosilicon alloy with a particle size of 5-10 ⁇ m.
  • the active material includes ferrosilicon alloy nanosheets, carbon-coated tin nanowires and carbon nanotubes, and the surface of the ferrosilicon alloy nanosheets is coated with a carbon layer.
  • the thickness of ferrosilicon alloy nanosheets is 20-60nm, and the planar size is 100-500nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10 -20nm, aspect ratio is (100-200):1.
  • silicon accounts for 76.3wt% of active materials; iron accounts for 12.1wt% of active materials, tin accounts for 3.5wt% of active materials; carbon accounts for 7.6wt% of active materials; other substances account for 0.5% of active materials. wt%.
  • Embodiment 4 The difference between Embodiment 4 and Embodiment 1 is that in step (1), the solar silicon wafer cutting waste is replaced with silicon nanosheets with a thickness of 10-50nm and a planar size of 100-600nm, and does not need to be sanded in a sand mill. grind.
  • the active materials include silicon nanosheets, carbon-coated tin nanowires and carbon nanotubes.
  • the thickness of silicon nanosheets is 10-50nm, and the planar size is 100-600nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10- 20nm, aspect ratio is (100-200):1.
  • silicon accounts for 87.6wt% of the active material; tin accounts for 4.3wt% of the active material; carbon accounts for 7.8wt% of the active material; and other substances account for 0.3wt% of the active material.
  • Embodiment 5 The difference between Embodiment 5 and Embodiment 1 is that in step (2), the solar silicon wafer cutting waste is replaced with silicon oxide nanosheets with a thickness of 50-100nm and a planar size of 100-800nm. There is no need to use a sand mill. Medium sanding.
  • the active materials include silicon oxide nanosheets, carbon-coated tin nanowires and carbon nanotubes.
  • the thickness of silicon oxide nanosheets is 50-100nm, and the planar size is 100-800nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10-20nm, aspect ratio is (100-200):1.
  • silicon accounts for 61.2wt% of the active material; oxygen accounts for 28.5wt% of the active material; tin accounts for 3.6wt% of the active material; carbon accounts for 4.2wt% of the active material; other substances account for 3.1wt of the active material. %.
  • Embodiment 5 The difference between Embodiment 5 and Embodiment 1 is that: in step (2), the solar silicon wafer cutting waste is replaced with ferrosilicon alloy nanosheets with a thickness of 50-80nm and a planar size of 200-600nm, and does not need to be used in a sand mill. Sanding.
  • the active materials include ferrosilicon alloy nanosheets, carbon-coated tin nanowires and carbon nanotubes.
  • the thickness of ferrosilicon alloy nanosheets is 50-80nm, and the planar size is 200-600nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10 -20nm, aspect ratio is (100-200):1.
  • silicon accounts for 74.6wt% of active materials; iron accounts for 11.5wt% of active materials, tin accounts for 3.2wt% of active materials; carbon accounts for 7.6wt% of active materials; other substances account for 2.1% of active materials. wt%.
  • Example 7 The difference between Example 7 and Example 1 is that in step (2), the solar silicon wafer cutting waste is replaced with single crystal silicon with a particle size of 5-10 ⁇ m.
  • the active material includes silicon nanosheets, carbon-coated tin nanowires and carbon nanotubes, and the surface of the silicon nanosheets is coated with a carbon layer.
  • the thickness of silicon nanosheets is 50-100nm, and the planar size is 200-1000nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10- 20nm, aspect ratio is (100-200):1.
  • silicon accounts for 84.6wt% of the active material; tin accounts for 5.1wt% of the active material; carbon accounts for 6.9wt% of the active material; and other substances account for 3.4wt% of the active material.
  • Example 8 The difference between Example 8 and Example 1 is that no carbon nanotubes and tin oxide are added.
  • the active material includes silicon nanosheets, and the surface of the silicon nanosheets is coated with a carbon layer.
  • the thickness of silicon nanosheets is 10-80nm, and the plane size is 200-800nm; in terms of weight percentage, silicon accounts for 94.6wt% of the active material; tin accounts for 0wt% of the active material; carbon accounts for 4.2wt% of the active material; Other substances account for 1.2 wt% of the active material.
  • Example 9 The difference between Example 9 and Example 1 is that the preparation method of the negative electrode material is:
  • the carbon nanotubes are dispersed in an ethanol solvent to obtain a carbon nanotube solution, where the mass ratio of the carbon nanotubes to ethanol is 1:100.
  • Example 10 The difference between Example 10 and Example 9 is that the preparation method of carbon-coated tin nanowires is: placing the tin nanowires in an N-methylpyrrolidone solution containing polytetrafluoroethylene, and after dispersing, the tin nanowires are coated on the surface. Covered with an adhesive layer; filter and dry to obtain the precursor. The precursor is put into a high-temperature sintering furnace and sintered and carbonized under a nitrogen atmosphere from room temperature to 700°C. After sintering, carbon-coated tin nanowires can be obtained.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the solar silicon wafer cutting waste is replaced with silicon powder with a diameter of 80-100 nm, and silicon nanosheets cannot be formed.
  • the active material does not have silicon nanosheets, only silicon nanoparticles with a diameter of 80-100nm, and the silicon surface is coated with a carbon layer.
  • the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500):1; the diameter of carbon nanotubes is 10-20nm, and the aspect ratio is (100-200). ):1.
  • silicon accounts for 84.3wt% of the active material; tin accounts for 5.3wt% of the active material; carbon accounts for 5.7wt% of the active material; and other substances account for 3.7wt% of the active material.
  • the size of the silicon-based nanosheets, the size of the carbon-coated tin nanowires, the size of the carbon nanotubes, and the arrangement of the silicon-based nanosheets were all observed through scanning electron microscopy (SEM) images.
  • Figure 1 is a scanning electron microscope (SEM) image of the negative pole piece (original pole piece) provided in Example 1 of the present application. Please refer to Figure 1. There are some gaps inside the original pole piece, and the pole piece has a certain porosity. Silicon nanoparticles There is a linear structure between the sheets, and the silicon nanosheets tend to be arranged in parallel to form a stacked structure, and they also tend to be arranged in parallel in the direction of the current collector.
  • Figure 2 is a scanning electron microscope (SEM) image of the negative electrode plate (in the fifth cycle of lithium insertion state) provided in Example 1 of the present application. Please refer to Figure 2.
  • SEM scanning electron microscope
  • Figure 3 is a scanning electron microscope (SEM) image of the negative pole piece (original pole piece) provided in Comparative Example 1. Please refer to Figure 3. There are some gaps inside the original pole piece, and the pole piece has a certain porosity. Among the silicon nanosheets There is a linear structure between them, and the silicon nanosheets are arranged irregularly.
  • Figure 4 is a scanning electron microscope (SEM) image of the negative electrode plate (in the fifth week of lithium insertion state) provided in Comparative Example 1. Please refer to Figure 4. Since the silicon nanosheets are irregularly arranged, during the lithium insertion process, the silicon nanosheets move along the Volume changes and sliding occur in the thickness direction, which cannot fill the internal gaps of the pole piece, and are randomly distributed in the active material layer.
  • SEM scanning electron microscope
  • Figure 5 is an X-ray diffraction (XRD) pattern of the active material provided in Example 1 of the application.
  • Figure 6 is an X-ray diffraction (XRD) pattern of the negative electrode plate provided in Example 1 of the application before rolling.
  • Figure 7 is The X-ray diffraction (XRD) pattern of the negative electrode sheet after rolling provided in Example 1 of the present application.
  • XRD X-ray diffraction
  • a layer of PVDF is first coated on the copper foil during the coating process. When testing XRD, the copper foil is first removed.
  • the values of the (111)/(220) crystal plane peak intensity and the (111)/(311) crystal plane peak intensity of the rolled pole piece both increase, indicating that the rolled pole piece has better performance. Silicon
  • the angle between the nanosheets and the negative electrode current collector is small, and the silicon nanosheets tend to be parallel to the negative electrode current collector.
  • Figure 8 is a charge-discharge curve of the half-cell provided in Embodiment 1 of the present application. It can be seen from Figure 8 that the first-cycle capacity of the half-cell provided in Embodiment 1 is as high as 3000 mAh/g, and the first-cycle Coulombic efficiency is as high as 90%.
  • Figure 9 is a scanning electron microscope (SEM) picture of the negative active material provided in Example 1 of the present application.
  • Figure 10 is a scanning electron microscope (SEM) picture of the negative active material provided in Example 9 of the present application.
  • Figure 11 is a SEM picture of the negative active material provided in Example 1 of the present application.
  • a scanning electron microscope (SEM) image of the negative electrode active material after 5 weeks of battery cycling is provided.
  • FIG. 12 is a scanning electron microscope (SEM) image of the negative electrode active material provided in Comparative Example 3.
  • the carbon-coated tin nanowires, silicon nanosheets and carbon nanotubes in the negative active materials of Examples 1 and 9 are mixed to form a three-dimensional network structure, and the negative electrode in Figure 9
  • the carbon-coated tin nanowires and carbon nanotubes of the active materials can be more evenly dispersed on the surface of the silicon nanosheets to form a three-dimensional ion conductive network structure on the surface of the silicon nanosheets; at the same time, in the negative active material provided in Figure 9, by oxidizing Tin nanoparticles are evenly dispersed on the surface of silicon nanosheets, and then carbon-coated tin nanowires are reduced and uniformly grown in situ, which can compensate for the particle conductivity of silicon, and combine carbon nanotubes and silicon nanosheets to form a three-dimensional conductive network to make the negative electrode active.
  • Figure 13 is a transmission electron microscope (TEM) image of the carbon-coated tin nanowire provided in Example 1 of the application
  • Figure 14 is a transmission electron microscope (TEM) image of the carbon-coated tin nanowire provided in Example 10 of the application.
  • TEM transmission electron microscope
  • the microstructure of the carbon layer coated on the surface of the tin nanowires in Example 1 is a parallel linear structure, and the distance between two adjacent linear structures is d 002 The value is 0.33564.
  • Figure 15 is an impedance diagram of the battery provided in Example 1 and Example 9 of the present application. It can be seen from Figure 15 that the impedance of the battery prepared from the negative active material provided in Example 9 is the same as that prepared from the negative active material provided in Example 1. The resistance of the obtained battery is 2.5 times, indicating that the negative active material provided in Example 1 has more excellent conductivity.
  • Figure 16 is a cycle performance diagram of the battery provided in Example 1 of the present application under 2C conditions. It can be seen from Figure 16 that the embodiment of this application 1The battery provided can cycle stably for 1000 cycles, and the capacity can be stabilized at 700mAh/g.
  • the cycle capacity retention rate of 100 cycles the charging capacity of the 100th cycle / the charging capacity of the first week ⁇ 100%.
  • Volume expansion rate in the first week Use a micrometer to measure the original pole piece thickness h1 and the thickness h2 of the fully lithium-embedded pole piece in the first week.
  • the charging specific capacity in the first week, Coulombic efficiency in the first week, Coulombic efficiency in the 100th week and cycle capacity retention rate data in the 100th week of each embodiment and comparative example are shown in Table 2.
  • the half-battery prepared using the negative electrode sheet provided in the embodiment of the present application has a charging capacity greater than 1500 mAh/g in the first week, a cycle retention rate greater than 90% after 100 weeks, and a volume expansion rate in the first week. Both are less than 130%, indicating better overall performance.
  • the volume expansion rate of the half-battery prepared using the negative electrode sheet provided in the comparative example is very high, and the cycle retention rate is low.
  • Example 9 Comparing Example 1 and Example 9, it can be seen that after the battery is prepared from the negative active material provided in Example 1, its first-week charging capacity and cycle rate are The ring retention rates are all high, indicating that after mixing silicon nanosheets and carbon nanotubes with tin oxide particles, acetylene gas is introduced under high temperature conditions for reaction, and carbon-coated tin nanowires with a high degree of graphitization can be formed. , making the mixing of the three more uniform, and obtaining a negative active material with better performance.
  • Example 9 Comparing Example 9 and Example 10, it can be seen that after the battery is prepared from the negative active material provided in Example 9, its first-week charging capacity and cycle retention rate are both higher. It shows that compared with Example 10 where the organic binder is directly carbonized on the surface of the tin nanowires to form a carbon layer, Example 9 can form carbon-coated tin nanowires with a higher degree of graphitization by passing acetylene gas under high temperature conditions. After subsequent mixing with silicon nanosheets and carbon nanotubes, the resulting negative active material has better performance.
  • the capacity retention rate under different rates is calculated by the following formula.
  • Rate capacity retention rate charging capacity at this rate/0.1C rate charging capacity ⁇ 100%.
  • the capacity retention rate of the half-battery prepared using the negative electrode sheet provided in the embodiment of the present application is greater than 65% at 1C rate; while the half-battery prepared using the negative electrode sheet provided in the comparative example has a capacity retention rate of more than 65%.
  • the capacity retention rate at 1C rate is basically less than 40%.
  • Example 9 Comparing Example 1 and Example 9, it can be seen that after the negative active material provided in Example 1 is used to prepare a battery, its rate performance is better, indicating that after mixing silicon nanosheets and carbon nanotubes with tin oxide particles, they are introduced under high temperature conditions.
  • the reaction of acetylene gas can form carbon-coated tin nanowires with a higher degree of graphitization and at the same time make the mixing of the three more uniform, resulting in a negative active material with better performance.
  • Example 9 Comparing Example 9 and Example 10, it can be seen that after the negative active material provided in Example 9 is used to prepare a battery, its rate performance is better. It shows that compared with Example 10 where the organic binder is directly carbonized on the surface of the tin nanowires to form a carbon layer, Example 9 can form carbon-coated tin nanowires with a higher degree of graphitization by passing acetylene gas under high temperature conditions. After subsequent mixing with silicon nanosheets and carbon nanotubes, the resulting negative active material has better performance.
  • Example 1 On the basis of Example 1, the ratio of solar silicon and tin, ball milling time, and silicon type were changed respectively, and other conditions remained unchanged.
  • the active material was prepared according to the method of Example 1, and then the active material was prepared according to Example 1. Batteries No. 1-13 were prepared using the button half cell method, and the charge and discharge cycle performance of the batteries were tested according to the electrochemical performance testing method. The results are shown in Table 4.
  • Table 5 shows the XRD patterns of the negative electrode sheet (the active material includes silicon nanosheets) before and after rolling and the raw materials provided in Example 1, and the XRD patterns of the negative electrode sheet (the active material includes silicon nanoparticles) before and after rolling and the raw materials provided in Comparative Example 3. analysis results.
  • Example 1 The non-rolled and rolled pole pieces of Example 1 and Comparative Example 3 were tested by X-ray diffraction. The results showed that in Example 1, from raw materials to pole pieces produced and then rolled, (111)/ The (220) crystal plane peak intensity and the (111)/(311) crystal plane peak intensity ratio are gradually increasing, indicating that the nanosheets in the pole piece gradually tend to be arranged in parallel, corresponding to SEM, while in Comparative Example 3, from raw materials to After making the pole piece and then rolling it, the peak intensity ratio of (111)/(220) crystal plane and the peak intensity of (111)/(311) crystal plane remain basically unchanged.

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Abstract

La présente demande concerne une feuille d'électrode négative, son procédé de préparation, une batterie et un procédé de préparation d'un matériau d'électrode négative, et appartient au domaine technique des batteries secondaires. La feuille d'électrode négative comprend un collecteur de courant d'électrode négative et une couche de matériau actif d'électrode négative disposée sur la surface du collecteur de courant d'électrode négative. Un matériau actif dans la couche de matériau actif d'électrode négative comprend des matériaux à base de silicium en forme de pièce, et en utilisant la surface du collecteur de courant d'électrode négative comme référence, l'angle inclus entre au moins 60 % des matériaux à base de silice en forme de pièce et la surface du collecteur de courant d'électrode négative est ≤20°. Les matériaux à base de silicium en forme de pièce de la feuille d'électrode négative tendent à être parallèles au collecteur de courant d'électrode négative et, dans la direction de l'épaisseur de la feuille d'électrode négative, les matériaux à base de silicium en forme de pièce tendent à être disposés en parallèle et à former une structure empilée, ce qui rend la structure plus stable. Pendant les processus de charge et de décharge, les matériaux à base de silicium en forme de pièce changent de volume et coulissent dans la direction de l'épaisseur, de manière à combler les espaces dans la feuille d'électrode négative, ce qui permet à la feuille d'électrode de présenter un contact électrique et une intégrité de qualité, et d'obtenir de meilleures performances de batterie.
PCT/CN2023/090928 2022-04-26 2023-04-26 Feuille d'électrode négative, son procédé de préparation, batterie et procédé de préparation de matériau d'électrode négative WO2023208058A1 (fr)

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