WO2023206593A1 - 负极材料、负极极片及其制备方法和锂离子电池及其制备方法 - Google Patents

负极材料、负极极片及其制备方法和锂离子电池及其制备方法 Download PDF

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WO2023206593A1
WO2023206593A1 PCT/CN2022/091231 CN2022091231W WO2023206593A1 WO 2023206593 A1 WO2023206593 A1 WO 2023206593A1 CN 2022091231 W CN2022091231 W CN 2022091231W WO 2023206593 A1 WO2023206593 A1 WO 2023206593A1
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negative electrode
silicon
carbon
electrode material
material according
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PCT/CN2022/091231
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English (en)
French (fr)
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金周
黄学杰
闫勇
王丕涛
胡保平
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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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Priority claimed from CN202210446202.3A external-priority patent/CN114937772B/zh
Priority claimed from CN202210446207.6A external-priority patent/CN114944465A/zh
Application filed by 松山湖材料实验室, 中国科学院物理研究所 filed Critical 松山湖材料实验室
Publication of WO2023206593A1 publication Critical patent/WO2023206593A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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

Definitions

  • the present application relates to the technical field of lithium-ion battery materials, and in particular to a negative electrode material, a negative electrode plate and a lithium-ion battery.
  • 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.
  • the volume of silicon expands by more than 300% during the lithium storage process, which easily causes the powdering of silicon particles, causing the active material to fall off from the current collector, resulting in poor cycle stability of the electrode. amplitude decreased.
  • the purpose of the embodiments of the present application at least includes, for example, providing a negative electrode material, a negative electrode plate and a lithium-ion battery, so that the battery has a larger specific capacity and at the same time improves cycle stability. Also higher.
  • embodiments of the present application provide a negative electrode material, including silicon-based material, carbon-coated tin nanowires, and carbon nanotubes.
  • Carbon-coated nanowires and carbon nanotubes have a certain length, and have certain flexibility and elasticity. After being mixed with silicon-based materials, they can form a three-dimensional conductive network structure, which can alleviate the volume effect of lithium deintercalation in the negative electrode material, making The battery has a larger specific capacity and higher cycle stability; at the same time, the negative electrode material has good ionic conductivity and electronic conductivity, and better conductivity.
  • the silicon-based material includes at least one of elemental silicon, silicon alloy, and silicon oxide.
  • elemental silicon includes at least one of silicon nanoparticles, silicon nanosheets, and silicon nanowires.
  • the silicon alloy includes at least one of silicon aluminum alloy, silicon magnesium alloy, silicon ferro alloy and silicon silver alloy.
  • the particle size of the silicon nanoparticles is 5-200 nm.
  • the thickness of the silicon nanosheet is 5-100 nm, and the planar size is 100-2000 nm.
  • the silicon nanowire has a diameter of 5-200 nm and a length of 50-2000 nm.
  • the surface of the silicon-based material is also covered with a carbon layer with a thickness of nanometers.
  • the thickness of the carbon coating layer on the silicon-based material is 2-10 nm.
  • the diameter of the carbon-coated tin nanowire is below 100 nm, and the aspect ratio is (5-1000):1 (5:1-1000:1).
  • 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 nanotube is less than 20 nm, and the aspect ratio is (10-1000):1 (10:1-1000:1).
  • the carbon nanotubes include at least single-walled carbon nanotubes.
  • the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes.
  • the weight percentage of silicon in the negative electrode material is 60%-98%, the weight percentage of tin is 0.5%-20%, and the weight percentage of carbon is 1.5-20%. .
  • the negative electrode material further includes carbon powder.
  • the carbon powder is one or more of graphite, hard carbon, and soft carbon.
  • embodiments of the present application provide a negative electrode sheet, including the above negative electrode material.
  • embodiments of the present application provide a method for preparing a negative electrode sheet, including:
  • the negative electrode slurry is coated on the negative electrode current collector and dried to form a negative electrode sheet.
  • 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 method for preparing a lithium-ion secondary battery, including:
  • the electrode group is placed in the case and electrolyte is injected to form a lithium ion secondary battery.
  • embodiments of the present application provide a lithium-ion solid-state battery, including the above-mentioned negative electrode sheet.
  • embodiments of the present application provide a method for preparing a lithium-ion solid-state battery, including:
  • the above-described negative electrode sheet is combined with a positive electrode sheet and a solid electrolyte to form a lithium-ion solid-state battery.
  • Figure 1 is a schematic structural diagram of the negative electrode material provided by the embodiment of the present application.
  • Figure 2 is a scanning electron microscope (SEM) image of the negative electrode material provided in Example 1 of the present application;
  • Figure 3 is a transmission electron microscope (TEM) image of the negative electrode material provided in Example 1 of the present application.
  • Figure 4 is an electrochemical cycle diagram of a half-cell prepared from the negative electrode material provided in Example 1 of the present application.
  • Icon 110-silicon-based materials; 120-carbon-coated tin nanowires; 130-carbon nanotubes.
  • FIG. 1 is a schematic structural diagram of an anode material provided by an embodiment of the present application. Please refer to FIG. 1 .
  • the anode material includes a silicon-based material 110 , a carbon-coated tin nanowire 120 and a carbon nanotube 130 .
  • the schematic diagram in Figure 1 is a schematic diagram after the three are mixed.
  • the carbon-coated nanowires and carbon nanotubes 130 have a certain length, and have certain flexibility and elasticity. After being mixed with the silicon-based material 110, they can form a three-dimensional conductive network structure, which can alleviate the deintercalation of the negative electrode material.
  • the volume effect of lithium makes the battery have a larger specific capacity and higher cycle stability; at the same time, the negative electrode material has good ionic conductivity and electronic conductivity, and better conductivity.
  • the silicon-based material 110 refers to a silicon-based material 110 that contains silicon and is capable of deintercalating lithium.
  • the silicon-based material 110 includes at least one of elemental silicon, silicon alloy, and silicon oxide.
  • the silicon alloy includes at least one of silicon aluminum alloy, silicon magnesium alloy, ferrosilicon alloy and silicon silver alloy.
  • the size of the silicon-based material 110 may be in the nanoscale or micron scale; the silicon-based material 110 may be in the form of granules, sheets, lines, etc.
  • elemental silicon includes at least one of silicon nanoparticles, silicon nanosheets, and silicon nanowires.
  • silicon nanoparticles refer to: silicon element is in the form of granules, and the particle size of the silicon particles is nanoscale.
  • the particle size of the silicon nanoparticles is 5-200 nm.
  • the particle size of silicon nanoparticles refers to the size with the largest outer diameter of silicon nanoparticles.
  • the particle size of silicon nanoparticles is 5nm, 10nm, 20nm, 40nm, 80nm, 120nm, 160nm or 200nm.
  • Silicon nanosheets refer to silicon as a flake, and the thickness of the silicon wafer is nanometer-scale.
  • the silicon nanosheet has a thickness of 5-100nm and a planar size of 100-2000nm.
  • 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 5nm, 10nm, 20nm, 40nm, 60nm, 80nm or 100nm;
  • the plane size of silicon nanosheets is 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200nm, 1400nm, 1600nm, 1800nm or 2000nm. .
  • Silicon nanowires refer to silicon elements in the form of wires, and the diameter of the silicon wires is nanoscale.
  • the diameter of silicon nanowires is 5-200nm and the length is 50-2000nm.
  • the diameter of the silicon nanowire is: the largest diameter value in different areas of the silicon nanowire.
  • the diameter of silicon nanowire is 5nm, 10nm, 20nm, 40nm, 80nm, 120nm, 160nm or 200nm; the length is 50nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200nm, 1400nm, 1600nm, 1800nm or 2000nm.
  • the surface of the silicon-based material 110 is also covered with a carbon layer with a thickness of nanometers.
  • the thinner carbon layer can maintain a higher specific capacity of the negative electrode material;
  • the coating of the carbon layer can make the surface of the silicon-based material 110 a material with good conductivity, which is consistent with the carbon-coated tin nanowires.
  • 120 and carbon nanotubes 130 can form a negative electrode material with a better conductive network, making the entire negative electrode material better conductive;
  • the carbon layer can avoid direct contact between the silicon-based material 110 and the electrolyte to a certain extent.
  • the cycle stability of the anode material is further improved.
  • the thickness of the carbon coating layer on the silicon-based material 110 is 2-10 nm.
  • the carbon-coated tin nanowire 120 means that the surface of the tin nanowire is coated with a carbon layer, and the formed carbon-coated tin nanowire 120 is still a linear structure, and its size is 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 120 is nanoscale.
  • the thickness of the carbon coating layer on the carbon-coated tin nanowire 120 is 2-10 nm.
  • the diameter of the carbon-coated tin nanowire 120 is below 100 nm, and the aspect ratio is (5-1000):1.
  • the diameters of different parts of the carbon-coated tin nanowire 120 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.
  • the aspect ratio of the carbon-coated tin nanowire 120 is 5:1, 10:1, 20:1, 40:1, 80:1, 160:1, 320:1, 480:1, 600: 1 or 1000:1.
  • the nano-layer spacing refers to the layer spacing (unit: nm) of the carbon coating layer on the (002) crystal plane.
  • the graphitization degree ⁇ of the carbon coating layer of the carbon-coated tin nanowire 120 is in the range of 0.3-1, and its graphitization degree is relatively high, which can make the anode material have higher efficiency and cycle performance.
  • the carbon nanotube 130 means that the carbon material is in the shape of a tube, and the outer diameter of the carbon tube is nanoscale.
  • the diameter of the carbon nanotube 130 is less than 20 nm, and the aspect ratio is (10-1000):1.
  • the diameters of different parts of the carbon nanotube 130 can be the same or different.
  • the diameter is below 20nm and the aspect ratio is (10-1000):1, which can make it more flexible and form better after being mixed with other materials.
  • the carbon nanotubes 130 at least include single-walled carbon nanotubes 130, which can improve the performance of the negative electrode material.
  • the carbon nanotubes 130 may also be a mixture of single-walled carbon nanotubes 130 and multi-walled carbon nanotubes 130 .
  • the weight percentage of silicon is 60%-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 weight percentage of the carbon of the carbon-coated tin nanowire 120 and the carbon of the carbon nanotube 130 .
  • the weight percentage of silicon refers to the weight percentage of silicon in the silicon-based material 110;
  • the weight percentage of tin refers to the weight percentage of tin in the carbon-coated tin nanowire 120.
  • the weight percentage of silicon is 60%, 65%, 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%;
  • the weight percentage of carbon is 1.5%, 3%, 5%, 8%, 10%, 12%, 14%, 16% , 18% or 20%.
  • the above-mentioned negative electrode material is a silicon-based negative electrode material, and the negative electrode material can also be mixed with a carbon-based negative electrode material.
  • the negative electrode material also includes carbon powder.
  • carbon powder can be one or more of graphite, hard carbon and soft carbon.
  • An embodiment of the present application also provides a negative electrode sheet, including the above negative electrode material.
  • the negative electrode piece includes all the technical features of the above-mentioned negative electrode material and can achieve the same beneficial technical effects as the above-mentioned negative electrode material. For details, please refer to the previous description of the negative electrode material, which will not be described again in this application.
  • Embodiments of the present application also provide a method for preparing the above-mentioned negative electrode sheet, wherein after the above-mentioned negative electrode material is mixed with a solvent, a conductive additive and a binder, a negative electrode slurry can be formed, and the negative electrode slurry is coated on the negative electrode current collector. , after drying, the negative electrode piece can be formed.
  • An embodiment of the present application also provides a lithium ion secondary battery, including the above-mentioned negative electrode piece.
  • This lithium ion secondary battery includes all the technical features of the above-mentioned negative electrode sheet and can achieve the same beneficial technical effects as the above-mentioned negative electrode material and the above-mentioned negative electrode sheet. For details, please refer to the previous description of the negative electrode material, which will not be described again in this application. .
  • Embodiments of the present application also provide a method for preparing the above-mentioned lithium ion secondary battery, in which the negative electrode sheet is combined with the positive electrode sheet and separator to form an electrode group.
  • the electrode group is placed in the casing and the electrolyte is injected into it to form Lithium-ion secondary battery.
  • An embodiment of the present application also provides a lithium-ion solid-state battery, including the above-mentioned negative electrode piece.
  • This lithium-ion solid-state battery includes all the technical features of the above-mentioned negative electrode sheet and can achieve the same beneficial technical effects as the above-mentioned negative electrode material and the above-mentioned negative electrode sheet. For details, please refer to the previous description of the negative electrode material, which will not be described again in this application.
  • Embodiments of the present application also provide a method for preparing the above-mentioned lithium-ion solid-state battery, wherein the negative electrode sheet, the positive electrode sheet and the solid electrolyte can be combined to form a lithium-ion solid-state battery.
  • 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.
  • step (1) Add silicon powder and polyvinylpyrrolidone (PVP) with a particle size of 5-10 ⁇ m to the carbon nanotube solution in step (1), homogeneously disperse it in a homogenizer, and sand-grind the homogeneously dispersed suspension. Sanding in the machine, after the sanding is completed, tin nanowires and PVP are added and dispersed in the homogenizer, and then filtered, washed, and dried to obtain a uniformly dispersed composite precursor. Finally, the composite precursor material is put into a high-temperature sintering furnace and sintered in a mixed atmosphere of nitrogen and acetylene from room temperature to 700°C. After sintering, the negative electrode material can be obtained.
  • PVP polyvinylpyrrolidone
  • step (2) Add the negative electrode material, conductive agent SP, and sodium alginate in step (2) to the water in a mass ratio of 80:5:15 and stir continuously to obtain a negative electrode slurry.
  • the negative electrode slurry is applied to the surface of the copper foil with a scraper, and then dried to obtain a negative electrode piece.
  • the negative electrode piece is cold-pressed, and the cold-pressed negative electrode piece is prepared into a small round piece with a diameter of 15 mm using a puncher.
  • 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).
  • the negative electrode material obtained in step (2) of Example 1 includes silicon nanoparticles, carbon-coated tin nanowires and carbon nanotubes.
  • the surface of silicon nanoparticles has a carbon coating layer; the particle size of silicon nanoparticles is 50-200nm; the diameter of carbon-coated tin nanowires is 20-80nm, and the aspect ratio is (50-500): 1; carbon nanotubes The diameter is 10-20nm, and the aspect ratio is (100-200):1.
  • silicon accounts for 82.4wt% of the negative electrode material; tin accounts for 5.6wt% of the negative electrode material; carbon accounts for 9.9wt% of the negative electrode material; and other substances account for 2.1wt% of the negative electrode material.
  • Example 2 The difference between Example 2 and Example 1 is that the silicon powder with a particle size of 5-10 ⁇ m is replaced with silicon oxide with a particle size of 5-10 ⁇ m, and the remaining steps are the same as in Example 1.
  • the negative electrode material of Example 2 includes silicon-based materials, carbon-coated tin nanowires and carbon nanotubes.
  • the silicon-based material is silicon-oxygen nanosheets and silicon-oxygen nanoparticles, and the surfaces of the silicon-oxygen nanosheets and silicon-oxygen nanoparticles have a carbon coating layer; the thickness of the silicon-oxygen nanosheets is 20-800nm, and the plane size is 200-500nm;
  • the particle size of silicon nanoparticles is 50-200nm; 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 63.5wt% of the negative electrode material; oxygen accounts for 30.5wt% of the negative electrode material; tin accounts for 3.4wt% of the negative electrode material; carbon accounts for 5.2wt% of the negative electrode material; and other substances account for 2.6wt of the negative electrode material. %.
  • Example 3 The difference between Example 3 and Example 1 is that in Example 1, the silicon powder with a particle size of 5-10 ⁇ m is replaced by a ferrosilicon alloy with a particle size of 5-10 ⁇ m, and the remaining steps are the same as in Example 1.
  • the negative electrode material of Example 3 includes silicon-based materials, carbon-coated tin nanowires and carbon nanotubes.
  • the silicon-based material is ferrosilicon alloy nanosheets and ferrosilicon alloy nanoparticles, and part of the surface of the ferrosilicon alloy nanosheets and ferrosilicon alloy nanoparticles has a carbon coating layer; the thickness of the ferrosilicon alloy nanosheets is 20-100nm, and the planar size is 100-600nm.
  • the particle diameter of ferrosilicon alloy nanoparticles is 5-200nm; 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 The ratio is (100-200):1.
  • silicon accounts for 76.6wt% of the negative electrode material; silicon accounts for 12.8wt% of the negative electrode material; tin accounts for 4.3wt% of the negative electrode material; carbon accounts for 5.5wt% of the negative electrode material; other substances account for 0.8% of the negative electrode material. wt%.
  • Example 4 The difference between Example 4 and Example 1 is that silicon powder with a particle size of 5-10 ⁇ m is replaced with solar silicon wafer cutting waste, and the remaining steps are the same as in Example 1.
  • the negative electrode material of Example 4 includes silicon nanosheets, carbon-coated tin nanowires and carbon nanotubes, and there is a carbon coating layer on the surface of the silicon nanosheets.
  • the thickness of silicon nanosheets is 10-80nm, and the plane size is 200-800nm; the particle size of silicon nanoparticles is 5-200nm; 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 85.6wt% of the negative electrode material
  • tin accounts for 4.8wt% of the negative electrode material
  • carbon accounts for 5.9wt% of the negative electrode material
  • other substances account for 3.7wt% of the negative electrode material.
  • 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.
  • step (2) Add the negative electrode material, conductive agent SP, and sodium alginate in step (2) to the water in a mass ratio of 80:5:15 and stir continuously to obtain a negative electrode slurry.
  • the negative electrode slurry is applied to the surface of the copper foil with a scraper, and then dried to obtain a negative electrode piece.
  • the negative electrode piece is cold-pressed, and the cold-pressed negative electrode piece is prepared into a small round piece with a diameter of 15 mm using a puncher.
  • 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).
  • the negative electrode material of Example 5 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 85.3wt% of the active material; tin accounts for 4.2wt% of the active material; carbon accounts for 8.3wt% of the active material; and other substances account for 2.2wt% of the active material.
  • step (2) Add the negative electrode material, conductive agent SP, and sodium alginate in step (2) to the water in a mass ratio of 80:5:15 and stir continuously to obtain a negative electrode slurry.
  • the negative electrode slurry is applied to the surface of the copper foil with a scraper, and then dried to obtain a negative electrode piece.
  • the negative electrode piece is cold-pressed, and the cold-pressed negative electrode piece is prepared into a small round piece with a diameter of 15 mm using a puncher.
  • 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).
  • the negative electrode material of Example 6 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 85.5wt% of the active material; tin accounts for 4.9wt% of the active material; carbon accounts for 5.5wt% of the active material; and other substances account for 4.1wt% of the active material.
  • step (1) Add silicon powder and polyvinylpyrrolidone (PVP) with a particle size of 50-120 nm to the dispersion solution of carbon nanotubes and carbon-coated tin nanowires in step (1), homogeneously disperse in a homogenizer, then filter and wash , after drying, a uniformly dispersed composite precursor is obtained. Finally, the composite precursor material is put into a high-temperature sintering furnace and sintered in a mixed atmosphere of nitrogen and acetylene from room temperature to 700°C. After sintering, the negative electrode material can be obtained.
  • PVP polyvinylpyrrolidone
  • step (2) Add the negative electrode material, conductive agent SP, and sodium alginate in step (2) to the water in a mass ratio of 80:5:15 and stir continuously to obtain a negative electrode slurry.
  • the negative electrode slurry is applied to the surface of the copper foil with a scraper, and then dried to obtain a negative electrode piece.
  • the negative electrode piece is cold-pressed, and the cold-pressed negative electrode piece is prepared into a small round piece with a diameter of 15 mm using a puncher.
  • the negative electrode sheet and the lithium sheet in step (3) and assemble them into a button-type half-cell.
  • 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). It has been determined that the negative electrode material of Example 7 includes silicon nanoparticles, carbon-coated tin nanowires and carbon nanotubes, and the surface of the silicon nanoparticles is coated with a carbon layer.
  • the diameter of silicon nanoparticles is 50-120nm, 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 4.9wt% of the active material; carbon accounts for 6.3wt% of the active material; and other substances account for 4.5wt% of the active material.
  • Example 8 The difference between Example 8 and Example 1 is that silicon powder with a particle size of 5-10 ⁇ m is replaced with silicon nanosheets with a thickness of 10-50 nm and a planar size of 100-600 nm. The remaining steps are the same as in Example 1.
  • the negative electrode material of Example 8 includes 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 83.8wt% of the negative electrode material; tin accounts for 5.1wt% of the negative electrode material; carbon accounts for 6.2wt% of the negative electrode material; and other substances account for 4.9wt% of the negative electrode material.
  • Example 9 The difference between Example 9 and Example 1 is that silicon powder with a particle size of 5-10 ⁇ m is replaced with silicon nanowires with a diameter of 5-200 nm and a length of 50-2000 nm. The remaining steps are the same as in Example 1.
  • the negative electrode material of Example 8 includes silicon nanowires, carbon-coated tin nanowires and carbon nanotubes.
  • the diameter of silicon nanowires is 5-200nm, and the length is 50-2000nm; 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, The aspect ratio is (100-200):1.
  • silicon accounts for 82.2wt% of the negative electrode material; tin accounts for 5.6wt% of the negative electrode material; carbon accounts for 6.9wt% of the negative electrode material; and other substances account for 5.3wt% of the negative electrode material.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that no carbon nanotubes and tin nanowires are added, and the remaining steps are the same as Example 1.
  • the negative electrode material obtained in Comparative Example 1 only includes silicon nanoparticles, and the surface of the silicon nanoparticles has a carbon coating layer; the particle size of the silicon nanoparticles is 50-200nm; in terms of weight percentage, silicon accounts for 50% of the negative electrode material. 95.3.wt%; carbon accounts for 3.8wt% of the negative electrode material; other substances account for 0.9wt% of the negative electrode material.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that no tin nanowires are added, and the remaining steps are the same as Example 1.
  • the negative electrode material obtained in Comparative Example 2 includes silicon nanoparticles and carbon nanotubes.
  • the surface of the silicon nanoparticles has a carbon coating layer; the particle size of the silicon nanoparticles is 50-200nm; the diameter of the carbon nanotubes is 10-20nm.
  • the aspect ratio is (100-200): 1; in terms of weight percentage, silicon accounts for 92.2wt% of the negative electrode material; carbon accounts for 6.7wt% of the negative electrode material; other substances account for 1.1wt% of the negative electrode material.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that no carbon nanotubes are added, and the remaining steps are the same as Example 1.
  • the negative electrode material obtained in Comparative Example 2 includes silicon nanoparticles and carbon-coated tin nanowires.
  • the surface of the silicon nanoparticles has a carbon coating layer; the particle size of the silicon nanoparticles is 50-200nm; the carbon-coated tin nanowires The diameter is 20-80nm, and the aspect ratio is (50-500): 1; in terms of weight percentage, silicon accounts for 89.2wt% of the negative electrode material; tin accounts for 4.3wt% of the negative electrode material; carbon accounts for 5.7% of the negative electrode material wt%; other substances account for 0.8wt% of the negative electrode material.
  • step (2) solar silicon wafer cutting waste and polyvinylpyrrolidone (PVP) are added to the carbon nanotube solution in step (1) and homogeneously dispersed in a homogenizer. , then filter, wash, and dry to obtain a uniformly dispersed composite precursor. Finally, the composite precursor material is put into a high-temperature sintering furnace and sintered from room temperature to 700°C in a mixed atmosphere of nitrogen and acetylene. After sintering, it is dispersed in an ethanol solvent to obtain a dispersant, and tin nanowires are added to the homogenizer.
  • the negative electrode material can be obtained by homogeneously dispersing, filtering, washing and drying. , the remaining steps are the same as in Example 1
  • the negative electrode materials of Comparative Example 5 include silicon-based materials, tin nanowires and carbon nanotubes.
  • Silicon-based materials include 1-10um random silicon particles, with a carbon coating layer on the surface; the diameter of 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 87.8wt% of the negative electrode material; tin accounts for 4.1wt% of the negative electrode material; carbon accounts for 4.8wt% of the negative electrode material; and other substances account for 3.3wt% of the negative electrode material.
  • step (2) silicon powder and polyvinylpyrrolidone (PVP) with a particle size of 5-10 ⁇ m are added to the carbon nanotube solution in step (1) in a homogenizer. homogeneously dispersed in the medium, and then filtered, washed, and dried to obtain a uniformly dispersed composite precursor. Finally, the composite precursor material is put into a high-temperature sintering furnace and sintered from room temperature to 700°C in a mixed atmosphere of nitrogen and acetylene. After sintering, it is dispersed in an ethanol solvent to obtain a dispersant, and tin nanowires are added to the homogenizer.
  • the negative electrode material can be obtained by homogeneously dispersing, filtering, washing and drying. , the remaining steps are the same as in Example 1
  • the negative electrode material of Comparative Example 5 included mixed silicon-based materials, tin nanowires and carbon nanotubes.
  • Silicon-based materials include 5-10um silicon particles, with a carbon coating layer on the surface; the diameter of 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 89.3wt% of the negative electrode material; tin accounts for 4.1wt% of the negative electrode material; carbon accounts for 4.2wt% of the negative electrode material; and other substances account for 2.4wt% of the negative electrode material.
  • the cycle capacity retention rate of 100 cycles the charging capacity of the 100th cycle / the charging capacity of the first week ⁇ 100%.
  • 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 1.
  • the half-battery prepared using the negative electrode material provided in the embodiments of the present application has a first-week charging capacity greater than 2500 mAh/g, a first-week Coulombic efficiency greater than 87%, and a 100-week cycle capacity retention rate. Both are greater than 78%, indicating better overall performance.
  • the half-cell prepared using the anode material provided in the comparative example usually has poor cycle stability.
  • 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%.
  • Example 1 96.82 86.26 65.62 94.56
  • Example 2 95.36 86.16 65.26 94.53
  • Example 3 93.72 81.26 60.62 91.56
  • Example 4 96.54 89.78 68.95 97.12
  • Example 5 98.23 91.21 73.54 97.56
  • Example 6 98.25 92.15 73.61 97.63
  • Example 7 93.72 81.26 60.62 91.56
  • Example 8 97.36 90.16 71.26 96.53
  • Comparative example 1 83.14 45.31 19.65 56.32
  • Comparative example 2 82.25 54.31 25.94 75.14
  • Comparative example 3 81.28 50.52 21.85 70.15
  • Comparative example 4 85.22 49.21 23.84 53.17 Comparative example 5 80.54 48.33 22.39 52.29
  • the capacity retention rate of half cells prepared using the negative electrode materials provided in the examples of the present application is basically greater than 60% at 1C rate; while the half cells prepared using the negative electrode materials provided in the comparative examples have a capacity retention rate of 1C
  • the capacity retention rate under magnification is basically less than 30%.
  • FIG. 2 is a scanning electron microscope (SEM) picture of the negative electrode material provided in Example 1 of the present application
  • Figure 3 is a transmission electron microscope (TEM) picture of the negative electrode material provided in Example 1 of the present application.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • carbon-coated tin nanowires and carbon nanotubes are distributed on and between the surface of flake and granular silicon.
  • the inventor speculates that because the carbon-coated tin nanowires and carbon nanotubes have a certain length, and have good flexibility and elasticity, the carbon-coated tin nanowires can maintain structural integrity during the charge and discharge process, and at the same time can make the negative electrode active. Materials come into contact with each other, allowing for good electrical contact.
  • tin has excellent ionic conductivity
  • carbon nanotubes have excellent electronic conductivity, which can greatly improve the electrical performance of the half-cell.
  • Figure 4 is an electrochemical cycle diagram of a half-battery prepared from the anode material provided in Example 1 of the present application.
  • the first-week charging capacity of the half-battery provided in Example 1 is as high as 2728mAh/g, and the charging capacity for 100 cycles is as high as 2728mAh/g.
  • the cycle capacity retention rate is 81.26%, showing excellent electrochemical performance.
  • the negative electrode materials provided by this application include silicon-based materials, carbon-coated tin nanowires and carbon nanotubes. Carbon-coated nanowires and carbon nanotubes have a certain length, and have certain flexibility and elasticity. After being mixed with silicon-based materials, they can form a three-dimensional conductive network structure, which can alleviate the volume effect of lithium deintercalation in the negative electrode material, making The battery has a larger specific capacity and higher cycle stability; at the same time, the negative electrode material has good ionic conductivity and electronic conductivity, and better conductivity.

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Abstract

本申请涉及一种负极材料、负极极片及锂离子电池，属于锂离子电池材料技术领域。该负极材料包括硅基材料、碳包覆锡纳米线和碳纳米管。碳包覆纳米线和碳纳米管具有一定的长度，并且具有一定的柔韧性和弹性，其与硅基材料混合以后，可以形成三维导电网络结构，可以缓解负极材料脱嵌锂的体积效应，使电池的比容量较大、循环稳定性较高；同时，负极材料具有很好的离子导电率和电子导电率，导电能力更好。

Description

负极材料、负极极片及其制备方法和锂离子电池及其制备方法
相关申请的交叉引用
本申请要求于2022年04月26日提交中国专利局的申请号为2022104462023、名称为“负极材料、负极极片及锂离子电池”的中国专利申请以及于2022年04月26日提交中国专利局的申请号为2022104462076、名称为“负极极片及电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及锂离子电池材料技术领域，且特别涉及一种负极材料、负极极片及锂离子电池。
背景技术
由于便携式电子设备和电动汽车的快速发展和广泛应用，对于高比能量、长循环寿命的锂离子电池的需求十分迫切。目前商品化使用的锂离子电池主要采用石墨作为负极材料，但是，石墨的理论比容量仅为372mAh/g，限制了锂离子电池比能量的进一步提高。
而硅的理论比容量最高可以达到4200mAh/g，但是，硅在储锂过程中体积膨胀超过300％，容易造成硅颗粒的粉化，引起活性材料从集流体脱落，导致电极的循环稳定性大幅度下降。
发明内容
针对现有技术的至少一个不足之处，本申请实施例的目的至少包括例如提供一种负极材料、负极极片及锂离子电池，以使电池的比容量较大的同时，能够使循环稳定性也较高。
第一方面，本申请实施例提供了一种负极材料，包括硅基材料、碳包覆锡纳米线和碳纳米管。
碳包覆纳米线和碳纳米管具有一定的长度，并且具有一定的柔韧性和弹性，其与硅基材料混合以后，可以形成三维导电网络结构，可以缓解负极材料脱嵌锂的体积效应，使电池的比容量较大、循环稳定性较高；同时，负极材料具有很好的离子导电率和电子导电率，导电能力更好。
在本申请的部分实施例中，硅基材料包括单质硅、硅合金、氧化亚硅的至少一种。
在本申请的部分实施例中，单质硅包括硅纳米颗粒、硅纳米片、硅纳米线中的至少一种。
在本申请的部分实施例中，硅合金包括硅铝合金、硅镁合金、硅铁合金和硅银合金中的至少一种。
在本申请的部分实施例中，硅纳米颗粒的粒径为5-200nm。
在本申请的部分实施例中，硅纳米片的厚度为5-100nm，平面尺寸为100-2000nm。
在本申请的部分实施例中，硅纳米线的直径为5-200nm，长度为50-2000nm。
在本申请的部分实施例中，硅基材料的表面还包覆有厚度为纳米级的碳层。
在本申请的部分实施例中，硅基材料上的碳包覆层的厚度为2-10nm。
在本申请的部分实施例中，碳包覆锡纳米线的直径在100nm以下，长径比为(5-1000):1(5:1-1000:1)。
在本申请的部分实施例中，碳包覆锡纳米线中碳包覆层的厚度为纳米级。
在本申请的部分实施例中，碳包覆锡纳米线上的碳包覆层的厚度为2-10nm。
在本申请的部分实施例中，碳包覆锡纳米线中碳包覆层的石墨化度γ满足0.3≦γ≦1，其中γ＝(0.344-d 002)/(0.344-0.3354)，d 002为碳包覆层在002晶面的纳米层间距。
在本申请的部分实施例中，碳纳米管的直径在20nm以下，长径比为(10-1000):1(10:1-1000:1)。
在本申请的部分实施例中，碳纳米管至少包括单壁碳纳米管。
在本申请的部分实施例中，碳纳米管是单壁碳纳米管和多壁碳纳米管的混合物。
在本申请的部分实施例中，负极材料中，硅的重量百分含量为60％-98％，锡的重量百分含量为0.5％-20％，碳的重量百分含量为1.5-20％。
在本申请的部分实施例中，负极材料还包括碳粉。
在本申请的部分实施例中，碳粉是石墨、硬碳和软碳中的一种或多种。
第二方面，本申请实施例提供了一种负极极片，包括上述负极材料。
第三方面，本申请实施例提供了一种负极极片的制备方法，包括：
将上述负极材料与溶剂、导电添加剂和粘结剂混合以形成负极浆料；
将该负极浆料涂覆在负极集流体上，干燥以形成负极极片。
第四方面，本申请实施例提供了一种锂离子二次电池，包括上述负极极片。
第五方面，本申请实施例提供了一种锂离子二次电池的制备方法，包括：
将上述负极极片与正极极片和隔膜组合以形成电极组；
将该电极组置于壳体内，并注入电解液，以形成锂离子二次电池。
第六方面，本申请实施例提供了一种锂离子固态电池，包括上述负极极片。
第七方面，本申请实施例提供了一种锂离子固态电池的制备方法，包括：
将上述负极极片与正极极片和固态电解质组合，以形成锂离子固态电池。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请实施例提供的负极材料的结构示意图；
图2为本申请实施例1提供的负极材料的扫描电镜(SEM)图；
图3为本申请实施例1提供的负极材料的透射电镜(TEM)图；
图4为本申请实施例1提供的负极材料制备得到的半电池的电化学循环图。
图标：110-硅基材料；120-碳包覆锡纳米线；130-碳纳米管。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面对本申请的技术方案进行清楚、完整地描述。
图1为本申请实施例提供的负极材料的结构示意图，请参阅图1，该负极材料包括硅基材料110、碳包覆锡纳米线120和碳纳米管130。图1中的示意图是三者混合以后的示意图。
可选地，碳包覆纳米线和碳纳米管130具有一定的长度，并且具有一定的柔韧性和弹性，其与硅基材料110混合以后，可以形成三维导电网络结构，可以缓解负极材料脱嵌锂的体积效应，使电池的比容量较大、循环稳定性较高；同时，负极材料具有很好的离子导电率和电子导电率，导电能力更好。
其中，硅基材料110是指含有硅，并且能够实现脱嵌锂的硅基材料110，例如：硅基材料110包括单质硅、硅合金、氧化亚硅的至少一种。硅合金包括硅铝合金、硅镁合金、硅铁合金和硅银合金中的至少一种。
硅基材料110的尺寸可以是纳米级，也可以是微米级；硅基材料110可以是颗粒状、片状、线状等。以单质硅为例，单质硅包括硅纳米颗粒、硅纳米片、硅纳米线中的至少一种。
其中，硅纳米颗粒是指：硅单质为颗粒状，该硅颗粒的粒径尺寸为纳米级。可选地，硅纳米颗粒的粒径为5-200nm。其中，硅纳米颗粒的粒径是指：硅纳米颗粒的外径最 大的尺寸。例如：硅纳米颗粒的粒径为5nm、10nm、20nm、40nm、80nm、120nm、160nm或200nm。
硅纳米片是指：硅单质为片状，该硅片的厚度为纳米级。可选地，硅纳米片的厚度为5-100nm，平面尺寸为100-2000nm。其中，硅纳米片的厚度是指：硅纳米片的两个表面之间的最大距离；硅纳米片的平面尺寸是指：该片状结构的硅纳米片在水平面上的投影的轮廓线中，距离最远的两个点之间的距离。例如：硅纳米片的厚度为5nm、10nm、20nm、40nm、60nm、80nm或100nm；硅纳米片的平面尺寸为100nm、200nm、400nm、600nm、800nm、1000nm、1200nm、1400nm、1600nm、1800nm或2000nm。
硅纳米线是指：硅单质为线状，该硅线的直径为纳米级。硅纳米线的直径为5-200nm，长度为50-2000nm。硅纳米线的直径为：硅纳米线的不同区域，直径最大的数值。例如：硅纳米线的直径为5nm、10nm、20nm、40nm、80nm、120nm、160nm或200nm；长度为50nm、100nm、200nm、400nm、600nm、800nm、1000nm、1200nm、1400nm、1600nm、1800nm或2000nm。
可选地，硅基材料110的表面还包覆有厚度为纳米级的碳层。一方面，碳层较薄，能够保持负极材料较高的比容量；另一方面，碳层的包覆，可以使硅基材料110的表面具有导电性良好的材料，与碳包覆锡纳米线120以及碳纳米管130配合，可以形成导电网络更好的负极材料，使整个负极材料的导电性能更佳；第三方面，碳层可以在一定程度上避免硅基材料110与电解液直接接触，负极材料的循环稳定性进一步提高。可选地，硅基材料110上的碳包覆层的厚度为2-10nm。
其中，碳包覆锡纳米线120是指：锡纳米线的表面包覆有碳层，形成的碳包覆锡纳米线120依然是线状结构，且其尺寸也是纳米级。锡材料本身具有很好的导电性和离子导电能力，与包覆碳层配合以后，具有快速充放电能力；且碳层的包覆可以使其在充放电过程中的结构保持完整，并实现良好的电接触。可选地，碳包覆锡纳米线120中碳包覆层的厚度为纳米级。可选地，碳包覆锡纳米线120上的碳包覆层的厚度为2-10nm。
可选地，碳包覆锡纳米线120的直径在100nm以下，长径比为(5-1000):1。碳包覆锡纳米线120的不同部位的直径可以相同，也可以不同，直径在100nm以下且长径比为(5-1000):1，可以使其柔韧性更好，与其他材料混合以后，形成更好的三维导电网络。可选地，碳包覆锡纳米线120的长径比为5:1、10:1、20:1、40:1、80:1、160:1、320:1、480:1、600:1或1000:1。
可选地，碳包覆锡纳米线120中碳包覆层的石墨化度γ满足0.3≦γ≦1，其中γ＝(0.344-d 002)/(0.344-0.3354)，d 002为碳包覆层在002晶面的纳米层间距。其中，纳米层间距是指：碳包覆层在(002)晶面的层间距(单位为nm)。
可选地，碳包覆锡纳米线120的碳包覆层的石墨化度γ在0.3-1范围内，其石墨化程度较高，可以使负极材料具有更高的效率和循环性能。
其中，碳纳米管130是指：碳材料为管状，碳管的外径为纳米级。碳纳米管130的直径在20nm以下，长径比为(10-1000):1。碳纳米管130的不同部位的直径可以相同，也可以不同，直径在20nm以下且长径比为(10-1000):1，可以使其柔韧性更好，与其他材料混合以后，形成更好的三维导电网络。
可选地，碳纳米管130至少包括单壁碳纳米管130，可以使负极材料的性能更佳。可选地，碳纳米管130还可以是单壁碳纳米管130和多壁碳纳米管130的混合物。
本申请实施例的负极材料中，硅的重量百分含量为60％-98％，锡的重量百分含量为0.5％-20％，碳的重量百分含量为1.5-20％。其中，硅、锡和碳的重量百分含量是指元素含量，例如：碳的重量百分含量是指：碳包覆锡纳米线120的碳和碳纳米管130的碳的重量百分含量之和；硅的重量百分含量是指：硅基材料110中硅的重量百分含量；锡的重量百分含量是指：碳包覆锡纳米线120中锡的重量百分含量。
例如：硅的重量百分含量为60％、65％、70％、74％、78％、82％、86％、90％、94％或98％；锡的重量百分含量为0.5％、1％、2％、4％、8％、12％、16％或20％；碳的重量百分含量为1.5％、3％、5％、8％、10％、12％、14％、16％、18％或20％。
上述的负极材料为硅系负极材料，该负极材料还可以与碳系负极材料进行混合使用。可选地，负极材料还包括碳粉。例如：碳粉可以是石墨、硬碳和软碳中的一种或多种。
本申请实施例还提供了一种负极极片，包括上述负极材料。该负极极片包括上述负极材料的全部技术特征并且能够实现与上述负极材料相同的有益技术效果，具体可参见前文对负极材料的描述，本申请对此不再赘述。
本申请实施例还提供了一种上述负极极片的制备方法，其中上述负极材料与溶剂、导电添加剂和粘结剂混合以后，可以形成负极浆料，该负极浆料涂覆在负极集流体上，干燥以后，可以形成负极极片。
本申请实施例还提供了一种锂离子二次电池，包括上述负极极片。该锂离子二次电池包括上述负极极片的全部技术特征并且能够实现与上述负极材料与上述负极极片相同的有益技术效果，具体可参见前文对负极材料的描述，本申请对此不再赘述。
本申请实施例还提供了一种上述锂离子二次电池的制备方法，其中负极极片与正极极片和隔膜组合以后，形成电极组，该电极组置于壳体内，并注入电解液，形成锂离子二次电池。
本申请实施例还提供了一种锂离子固态电池，包括上述负极极片。该锂离子固态电池包括上述负极极片的全部技术特征并且能够实现与上述负极材料与上述负极极片相同的有益技术效果，具体可参见前文对负极材料的描述，本申请对此不再赘述。
本申请实施例还提供了一种上述锂离子固态电池的制备方法，其中该负极极片与正极极片和固态电解质组合以后，可以形成锂离子固态电池。
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
(1)碳纳米管溶液的制备：
将碳纳米管分散在乙醇溶剂中得到碳纳米管溶液，其中，碳纳米管与乙醇的质量比为1:100。
(2)负极材料的制备：
向步骤(1)中的碳纳米管溶液中加入粒径为5-10μm的硅粉、聚乙烯吡咯烷酮(PVP)在均质机中均质分散，将均质分散后的悬浊液在砂磨机中砂磨，砂磨完成后再加入锡纳米线和PVP在均质机中进行分散，然后过滤、洗涤、烘干后获得均匀分散的复合前驱体。最后将复合前驱体材料放入高温烧结炉中在氮气和乙炔混合气氛下从室温升到700℃烧结，烧结完后即可得到负极材料。
(3)负极极片的制备：
将步骤(2)的负极材料、导电剂SP、海藻酸钠按质量比80：5：15的比例添加在水中并不断搅拌得到负极浆料。将负极浆料用刮刀涂覆于铜箔表面，再经烘干处理得到负极极片。将负极极片进行冷压处理，将冷压后的负极极片用打孔器制备出直径为15mm小圆片。
(4)半电池的制备：
将步骤(3)的负极极片与锂片配对装配成扣式半电池，电池的装配过程在充满氩气的手套箱中进行。其中使用Celgard2300膜为隔离膜，电解液为1mol/L的LiPF 6溶解于EC:DMC:FEC(体积比4.8:4.8:0.4)的溶液。
经测定，实施例1的步骤(2)得到的负极材料包括硅纳米颗粒、碳包覆锡纳米线和碳纳米管。硅纳米颗粒的表面有碳包覆层；硅纳米颗粒的粒径为50-200nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的82.4wt％；锡占负极材料的5.6wt％；碳占负极材料的9.9wt％；其他物质占负极材料的2.1wt％。
实施例2
实施例2与实施例1的区别在于：将粒径为5-10μm的硅粉替换成粒径为5-10μm的氧化亚硅，其余步骤与实施例1相同。
经测定，实施例2的负极材料包括硅基材料、碳包覆锡纳米线和碳纳米管。硅基材料为硅氧纳米片和硅氧纳米颗粒，且硅氧纳米片和硅氧纳米颗粒的表面有碳包覆层；硅氧纳米片的厚度为20-800nm，平面尺寸为200-500nm；硅纳米颗粒的粒径为50-200nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的63.5wt％；氧占负极材料的30.5wt％锡占负极材料的3.4wt％；碳占负极材料的5.2wt％；其他物质占负极材料的2.6wt％。
实施例3
实施例3与实施例1的区别在于：将实施例1中将粒径为5-10μm的硅粉替换成粒径为5-10μm的硅铁合金，其余步骤与实施例1相同。
经测定，实施例3的负极材料包括硅基材料、碳包覆部分锡纳米线和碳纳米管。硅基材料为硅铁合金纳米片和硅铁合金纳米颗粒，且硅铁合金纳米片和硅铁合金纳米颗粒的部分表面有碳包覆层；硅铁合金纳米片的厚度为20-100nm，平面尺寸为100-600nm；硅铁合金纳米颗粒的粒径为5-200nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的76.6wt％；硅占负极材料的12.8wt％；锡占负极材料的4.3wt％；碳占负极材料的5.5wt％；其他物质占负极材料的0.8wt％。
实施例4
实施例4与实施例1的区别在于：将粒径为5-10μm的硅粉替换成太阳能硅片切割废料，其余步骤与实施例1相同。
经测定，实施例4的负极材料包括硅纳米片、碳包覆锡纳米线和碳纳米管，硅纳米片的表面有碳包覆层。硅纳米片的厚度为10-80nm，平面尺寸为200-800nm；硅纳米颗粒的粒径为5-200nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的85.6wt％；锡占负极材料的4.8wt％；碳占负极材料的5.9wt％；其他物质占负极材料的3.7wt％。
实施例5
(1)碳纳米管溶液的制备：
将碳纳米管分散在乙醇溶剂中得到碳纳米管溶液，其中，碳纳米管与乙醇的质量比为1:100。
(2)活性物质的制备：
向碳纳米管溶液中加入太阳能硅片切割废料、氧化锡、聚乙烯吡咯烷酮(PVP)在均质机中均质分散，将均质分散后的悬浊液在砂磨机中砂磨5h，然后过滤、洗涤、烘干后获得均匀分散的复合前驱体。最后将前驱体材料放入高温烧结炉中在氮气气氛下从室温升到700℃烧结，并通入乙炔气体进行碳包覆，烧结完后即可得到活性物质。
(3)负极极片的制备：
将步骤(2)的负极材料、导电剂SP、海藻酸钠按质量比80：5：15的比例添加在水中并不断搅拌得到负极浆料。将负极浆料用刮刀涂覆于铜箔表面，再经烘干处理得到负极极片。将负极极片进行冷压处理，将冷压后的负极极片用打孔器制备出直径为15mm小圆片。
(4)半电池的制备：
将步骤(3)的负极极片与锂片配对装配成扣式半电池，电池的装配过程在充满氩气的手套箱中进行。其中使用Celgard2300膜为隔离膜，电解液为1mol/L的LiPF 6溶解于EC:DMC:FEC(体积比4.8:4.8:0.4)的溶液。
经测定，实施例5的负极材料包括硅纳米片、碳包覆锡纳米线和碳纳米管，且硅纳米片表面包覆有碳层。硅纳米片的厚度为10-80nm，平面尺寸为200-800nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为 (100-200):1。按照重量百分含量计，硅占活性物质的85.3wt％；锡占活性物质的4.2wt％；碳占活性物质的8.3wt％；其他物质占活性物质的2.2wt％。
实施例6
(1)活性物质的制备：
将太阳能硅片切割废料、氧化锡、聚乙烯吡咯烷酮(PVP)、钼酸铵和硝酸镁在均质机中均质分散，将均质分散后的悬浊液在砂磨机中砂磨5h，然后过滤、洗涤、烘干后获得均匀分散的复合前驱体。最后将前驱体材料放入高温烧结炉中在氮气气氛下从室温升到700℃烧结，并通入乙炔气体进行碳包覆，烧结完后即可得到活性物质。
(2)负极极片的制备：
将步骤(2)的负极材料、导电剂SP、海藻酸钠按质量比80：5：15的比例添加在水中并不断搅拌得到负极浆料。将负极浆料用刮刀涂覆于铜箔表面，再经烘干处理得到负极极片。将负极极片进行冷压处理，将冷压后的负极极片用打孔器制备出直径为15mm小圆片。
(3)半电池的制备：
将步骤(3)的负极极片与锂片配对装配成扣式半电池，电池的装配过程在充满氩气的手套箱中进行。其中使用Celgard2300膜为隔离膜，电解液为1mol/L的LiPF 6溶解于EC:DMC:FEC(体积比4.8:4.8:0.4)的溶液。
经测定，实施例6的负极材料包括硅纳米片、碳包覆锡纳米线和碳纳米管，且硅纳米片表面包覆有碳层。硅纳米片的厚度为10-80nm，平面尺寸为200-800nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占活性物质的85.5wt％；锡占活性物质的4.9wt％；碳占活性物质的5.5wt％；其他物质占活性物质的4.1wt％。
实施例7
(1)碳纳米管溶液的制备：
将碳纳米管和碳包覆锡纳米线分散在乙醇溶剂中得到碳纳米管溶液，其中，碳纳米管与乙醇的质量比为1:100。
(2)负极材料的制备：
向步骤(1)中的碳纳米管和碳包覆锡纳米线分散溶液中加入粒径为50-120nm的硅粉、聚乙烯吡咯烷酮(PVP)在均质机中均质分散，然后过滤、洗涤、烘干后获得均匀 分散的复合前驱体。最后将复合前驱体材料放入高温烧结炉中在氮气和乙炔混合气氛下从室温升到700℃烧结，烧结完后即可得到负极材料。
(3)负极极片的制备：
将步骤(2)的负极材料、导电剂SP、海藻酸钠按质量比80：5：15的比例添加在水中并不断搅拌得到负极浆料。将负极浆料用刮刀涂覆于铜箔表面，再经烘干处理得到负极极片。将负极极片进行冷压处理，将冷压后的负极极片用打孔器制备出直径为15mm小圆片。
(4)半电池的制备：
将步骤(3)的负极极片与锂片配对装配成扣式半电池，电池的装配过程在充满氩气的手套箱中进行。其中使用Celgard2300膜为隔离膜，电解液为1mol/L的LiPF 6溶解于EC:DMC:FEC(体积比4.8:4.8:0.4)的溶液。经测定，实施例7的负极材料包括硅纳米颗粒、碳包覆锡纳米线和碳纳米管，且硅纳米颗粒表面包覆有碳层。硅纳米颗粒直径为50-120nm，碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占活性物质的84.3wt％；锡占活性物质的4.9wt％；碳占活性物质的6.3wt％；其他物质占活性物质的4.5wt％。
实施例8
实施例8与实施例1的区别在于：将粒径为5-10μm的硅粉替换成厚度为10-50nm；平面尺寸为100-600nm的硅纳米片，其余步骤与实施例1相同。
经测定，实施例8的负极材料包括硅纳米片、碳包覆锡纳米线和碳纳米管。硅纳米片的厚度为10-50nm，平面尺寸为100-600nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的83.8wt％；锡占负极材料的5.1wt％；碳占负极材料的6.2wt％；其他物质占负极材料的4.9wt％。
实施例9
实施例9与实施例1的区别在于：将粒径为5-10μm的硅粉替换成直径为5-200nm，长度为50-2000nm的硅纳米线，其余步骤与实施例1相同。
经测定，实施例8的负极材料包括硅纳米线、碳包覆锡纳米线和碳纳米管。硅纳米线直径为5-200nm，长度为50-2000nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计， 硅占负极材料的82.2wt％；锡占负极材料的5.6wt％；碳占负极材料的6.9wt％；其他物质占负极材料的5.3wt％。
对比例1
对比例1与实施例1的区别在于：没有添加碳纳米管和锡纳米线，其余步骤与实施例1相同。
经测定，对比例1得到的负极材料只包括硅纳米颗粒，硅纳米颗粒的表面有碳包覆层；硅纳米颗粒的粒径为50-200nm；按照重量百分含量计，硅占负极材料的95.3.wt％；碳占负极材料的3.8wt％；其他物质占负极材料的0.9wt％。
对比例2
对比例2与实施例1的区别在于：没有添加锡纳米线，其余步骤与实施例1相同。
经测定，对比例2得到的负极材料包括硅纳米颗粒和碳纳米管，硅纳米颗粒的表面有碳包覆层；硅纳米颗粒的粒径为50-200nm；碳纳米管的直径为10-20nm、长径比为(100-200):1；按照重量百分含量计，硅占负极材料的92.2wt％；碳占负极材料的6.7wt％；其他物质占负极材料的1.1wt％。
对比例3
对比例3与实施例1的区别在于：没有添加碳纳米管，其余步骤与实施例1相同。
经测定，对比例2得到的负极材料包括硅纳米颗粒和碳包覆锡纳米线，硅纳米颗粒的表面有碳包覆层；硅纳米颗粒的粒径为50-200nm；碳包覆锡纳米线的直径为20-80nm，长径比为(50-500):1；按照重量百分含量计，硅占负极材料的89.2wt％；锡占负极材料的4.3wt％；碳占负极材料的5.7wt％；其他物质占负极材料的0.8wt％。
对比例4
对比例5与实施例1的区别在于：步骤(2)中，向步骤(1)中的碳纳米管溶液中加入太阳能硅片切割废料、聚乙烯吡咯烷酮(PVP)在均质机中均质分散，然后过滤、洗涤、烘干后获得均匀分散的复合前驱体。最后将复合前驱体材料放入高温烧结炉中在氮气和乙炔混合气氛下从室温升到700℃烧结，烧结完后分散在乙醇溶剂中得到分散剂，并加入锡纳米线在均质机中均质分散，然后过滤、洗涤、烘干后即可得到负极材料。，其余步骤与实施例1相同
经测定，对比例5负极材料包括硅基材料、锡纳米线和碳纳米管。硅基材料包括1-10um无规则硅颗粒，硅颗粒的表面有碳包覆层；锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计， 硅占负极材料的87.8wt％；锡占负极材料的4.1wt％；碳占负极材料的4.8wt％；其他物质占负极材料的3.3wt％。
对比例5
对比例5与实施例1的区别在于：步骤(2)中，向步骤(1)中的碳纳米管溶液中加入粒径为5-10μm的硅粉、聚乙烯吡咯烷酮(PVP)在均质机中均质分散，然后过滤、洗涤、烘干后获得均匀分散的复合前驱体。最后将复合前驱体材料放入高温烧结炉中在氮气和乙炔混合气氛下从室温升到700℃烧结，烧结完后分散在乙醇溶剂中得到分散剂，并加入锡纳米线在均质机中均质分散，然后过滤、洗涤、烘干后即可得到负极材料。，其余步骤与实施例1相同
经测定，对比例5负极材料包括混合的硅基材料、锡纳米线和碳纳米管。硅基材料包括5-10um硅颗粒，硅颗粒的表面有碳包覆层；锡纳米线的直径为20-80nm，长径比为(50-500):1；碳纳米管的直径为10-20nm、长径比为(100-200):1。按照重量百分含量计，硅占负极材料的89.3wt％；锡占负极材料的4.1wt％；碳占负极材料的4.2wt％；其他物质占负极材料的2.4wt％。
测试结果及分析
(1)初始性能与循环稳定性能
使用蓝电充放电测试仪对半电池进行恒电流充放电，其中截止电压设置为0.005-1.0V，倍率设定为0.2C，测试其首周充电容量、首周库伦效率、第100周充电容量、第100周库伦效率。
通过以下公式算出100周的循环容量保持率。
100周的循环容量保持率＝第100周的充电容量/首周的充电容量×100％。
各实施例和对比例首周充电比容量、首周库伦效率、第100周库伦效率及100周的循环容量保持率数据如表1所示。
表1半电池的初始性能与循环稳定性能
Figure PCTCN2022091231-appb-000001
Figure PCTCN2022091231-appb-000002
结合实施例和表1可知，使用本申请实施例提供的负极材料制备得到的半电池，其首周充电容量都大于2500mAh/g，首周库伦效率都大于87％、100周的循环容量保持率都大于78％，综合性能较佳。而使用对比例提供的负极材料制备的半电池，通常循环稳定性不好。
(2)倍率性能
使用蓝电充放电仪对半电池进行恒电流充放电，其中截止电压设置为0.005-1.0V，分别在0.1C、0.2C、0.5C、1C、0.2C倍率下进行测试。
通过以下公式不同倍率下容量保持率。
倍率容量保持率＝该倍率下的充电容量/0.1C倍率充电容量×100％。
各实施例和对比例不同倍率下容量保持率数据如表2所示。
表2半电池的倍率性能
  0.2C(％) 0.5C(％) 1C(％) 0.2C(％)
实施例1 96.82 86.26 65.62 94.56
实施例2 95.36 86.16 65.26 94.53
实施例3 93.72 81.26 60.62 91.56
实施例4 96.54 89.78 68.95 97.12
实施例5 98.23 91.21 73.54 97.56
实施例6 98.25 92.15 73.61 97.63
实施例7 93.72 81.26 60.62 91.56
实施例8 97.36 90.16 71.26 96.53
实施例9 95.36 86.16 65.26 94.53
对比例1 83.14 45.31 19.65 56.32
对比例2 82.25 54.31 25.94 75.14
对比例3 81.28 50.52 21.85 70.15
对比例4 85.22 49.21 23.84 53.17
对比例5 80.54 48.33 22.39 52.29
结合实施例和表2可知，使用本申请实施例提供的负极材料制备得到的半电池，其1C倍率下容量保持率基本都大于60％；而使用对比例提供的负极材料制备的半电池，1C倍率下容量保持率基本都小于30％。
图2为本申请实施例1提供的负极材料的扫描电镜(SEM)图；图3为本申请实施例1提供的负极材料的透射电镜(TEM)图。从图2和图3可以看出，碳包覆锡纳米线和碳纳米管分布在片状及颗粒状硅表面和之间。发明人推测，由于碳包覆锡纳米线和碳纳米管有一定的长度，并且有很好的柔韧性和弹性，碳包覆锡纳米线在充放电过程中结构保持完整，同时可以使负极活性物质之间相互接触，从而能够实现良好的电接触。尤其是锡具有优异的离子导电率，碳纳米管具有优异的电子导电率，可以大幅度提升半电池的电学性能。
图4为本申请实施例1提供的负极材料制备得到的半电池的电化学循环图，从图4可以看出，实施例1提供的半电池的首周充电容量高达2728mAh/g，100周的循环容量保持率为81.26％，表现出优异的电化学性能。
以上所描述的实施例是本申请一部分实施例，而不是全部的实施例。本申请的实施例的详细描述并非旨在限制要求保护的本申请的范围，而是仅仅表示本申请的选定实施 例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
工业实用性
本申请提供的负极材料包括硅基材料、碳包覆锡纳米线和碳纳米管。碳包覆纳米线和碳纳米管具有一定的长度，并且具有一定的柔韧性和弹性，其与硅基材料混合以后，可以形成三维导电网络结构，可以缓解负极材料脱嵌锂的体积效应，使电池的比容量较大、循环稳定性较高；同时，负极材料具有很好的离子导电率和电子导电率，导电能力更好。

Claims (19)

  1. 一种负极材料，其特征在于，包括硅基材料、碳包覆锡纳米线和碳纳米管。
  2. 根据权利要求1所述的负极材料，其特征在于，所述硅基材料包括单质硅、硅合金、氧化亚硅的至少一种；
    或/和，所述单质硅包括硅纳米颗粒、硅纳米片、硅纳米线中的至少一种；
    或/和，所述硅合金包括硅铝合金、硅镁合金、硅铁合金和硅银合金中的至少一种。
  3. 根据权利要求2所述的负极材料，其特征在于，所述硅纳米颗粒的粒径为5-200nm；
    或/和，所述硅纳米片的厚度为5-100nm，平面尺寸为100-2000nm。
  4. 根据权利要求2所述的负极材料，其特征在于，所述硅纳米线的直径为5-200nm，长度为50-2000nm。
  5. 根据权利要求1-3任一项所述的负极材料，其特征在于，所述硅基材料的表面还包覆有厚度为纳米级的碳层。
  6. 根据权利要求5所述的负极材料，其特征在于，所述硅基材料上的碳包覆层的厚度为2-10nm。
  7. 根据权利要求1-3任一项所述的负极材料，其特征在于，所述碳包覆锡纳米线的直径在100nm以下，长径比为(5-1000):1；
    或/和，所述碳包覆锡纳米线中碳包覆层的厚度为纳米级；
    或/和，所述碳包覆锡纳米线中碳包覆层的石墨化度γ满足0.3≦γ≦1，其中γ＝(0.344-d 002)/(0.344-0.3354)，d 002为碳包覆层在002晶面的纳米层间距。
  8. 根据权利要求7所述的负极材料，其特征在于，所述碳包覆锡纳米线上的所述碳包覆层的厚度为2-10nm。
  9. 根据权利要求1-3任一项所述的负极材料，其特征在于，所述碳纳米管的直径在20nm以下，长径比为(10-1000):1；
    或/和，所述碳纳米管至少包括单壁碳纳米管。
  10. 根据权利要求9所述的负极材料，其特征在于，所述碳纳米管是单壁碳纳米管和多壁碳纳米管的混合物。
  11. 根据权利要求1-3任一项所述的负极材料，其特征在于，所述负极材料中，硅的重量百分含量为60％-98％，锡的重量百分含量为0.5％-20％，碳的重量百分含量为1.5-20％。
  12. 根据权利要求1-3任一项所述的负极材料，其特征在于，所述负极材料还包括碳粉。
  13. 根据权利要求12所述的负极材料，其特征在于，所述碳粉是石墨、硬碳和软碳中的一种或多种。
  14. 一种负极极片，其特征在于，包括权利要求1-13任一项所述的负极材料。
  15. 一种根据权利要求14所述的负极极片的制备方法，其特征在于，包括：
    将所述负极材料与溶剂、导电添加剂和粘结剂混合以形成负极浆料；
    将所述负极浆料涂覆在负极集流体上，干燥以形成所述负极极片。
  16. 一种锂离子二次电池，其特征在于，包括权利要求14所述的负极极片。
  17. 一种根据权利要求16所述的锂离子二次电池的制备方法，其特征在于，包括：
    将所述负极极片与正极极片和隔膜组合以形成电极组；
    将所述电极组置于壳体内，并注入电解液，以形成所述锂离子二次电池。
  18. 一种锂离子固态电池，其特征在于，包括权利要求14所述的负极极片。
  19. 一种根据权利要求18所述的锂离子固态电池的制备方法，其特征在于，包括：
    将所述负极极片与正极极片和固态电解质组合，以形成所述锂离子固态电池。
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