WO2022012477A1 - 一种掺硅负极极片及包括该负极极片的锂离子电池 - Google Patents

一种掺硅负极极片及包括该负极极片的锂离子电池 Download PDF

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WO2022012477A1
WO2022012477A1 PCT/CN2021/105841 CN2021105841W WO2022012477A1 WO 2022012477 A1 WO2022012477 A1 WO 2022012477A1 CN 2021105841 W CN2021105841 W CN 2021105841W WO 2022012477 A1 WO2022012477 A1 WO 2022012477A1
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negative electrode
electrode active
active material
silicon
material layer
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French (fr)
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胡贤飞
余正发
宋博
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • 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 belongs to the technical field of lithium ion batteries, and in particular relates to a silicon-doped negative pole piece and a lithium ion battery including the negative pole piece.
  • a single-layer coating structure is generally adopted.
  • the feature of this structure is that the coating layer is evenly distributed throughout, but there are also certain problems. Due to the solid-phase diffusion rate of lithium in the silicon material It is lower than that of graphite, that is, the lithium insertion rate of silicon material is slower than that of graphite, which leads to the problem of lithium precipitation during charging of the negative electrode when silicon material is introduced. Therefore, it is particularly important to propose a silicon-doped anode sheet with higher anode gram capacity without deteriorating anode charging performance.
  • the present application uses a double-layer coating device to coat two layers of a first negative electrode active material layer and a second negative electrode active material layer with different compositions on both sides of the negative electrode current collector, wherein, in the first negative electrode active material layer
  • the inclusion of the first graphite and the first silicon material, and the inclusion of the second graphite in the second negative electrode active material layer enables the battery cell including the negative electrode pole piece to have higher energy density and cycle performance.
  • the OI value of the first graphite of the first negative electrode active material layer close to the negative electrode current collector is greater than the OI value of the second graphite of the second negative electrode active material layer away from the negative electrode current collector. This design can effectively improve the charging capacity of the negative electrode and further optimize the cycle performance of the cell.
  • a negative pole piece the negative pole piece comprises a negative electrode current collector, a first negative electrode active material layer and a second negative electrode active material layer, the first negative electrode active material layer is arranged on the surface of the negative electrode current collector, the second negative electrode active material layer The active material layer is arranged on the surface of the first negative electrode active material layer;
  • the first negative electrode active material layer includes a first negative electrode active material, and the first negative electrode active material includes a first graphite and a first silicon material;
  • the second negative electrode active material layer includes a second negative electrode active material, and the second negative electrode active material includes a second graphite;
  • the OI value represents the orientation index of graphite, and the smaller the OI value of graphite, the better the diffusion of lithium ions, and the lower the ultimate compaction density.
  • the anode slurry away from the current collector adopts graphite with a small OI value, which can effectively enhance the diffusion capacity of lithium ions and improve the charging performance of the anode.
  • the anode slurry close to the current collector uses graphite with a larger OI value, which can improve the compaction density of the anode sheet, thereby increasing the energy density of the battery.
  • the second negative electrode active material further includes a second silicon material; the mass ratio of the first silicon material in the first negative electrode active material layer is greater than the mass ratio of the second silicon material in the second negative electrode active material layer quality ratio.
  • the mass ratio of the first silicon material in the first negative electrode active material layer is 3-9 wt %
  • the mass ratio of the second silicon material in the second negative electrode active material layer is 3-9 wt %.
  • the proportion is 1-3wt%.
  • the mass ratio of the first silicon material in the first active material layer is 3-9 wt %
  • the mass ratio of the second silicon material in the second negative electrode material layer is 3-9 wt % is 0.
  • the negative electrode SEI grows continuously, consumes lithium ions and electrolyte, the negative electrode sheet thickens, and the active material falls off.
  • the macroscopic performance is that the capacity retention rate of the battery decays rapidly and the thickness expansion rate increases rapidly.
  • the high mass ratio of the first silicon material can improve the energy density of the battery; the low mass ratio of the second silicon material can ensure the charging and cycle performance of the second negative electrode active material layer of the negative electrode sheet, thereby improving the overall battery performance. cycle performance.
  • the sum of the mass of the first silicon material and the second silicon material accounts for 1-9 wt % of the total mass of the first negative electrode active material layer and the second negative electrode active material layer.
  • the ratio of the thickness of the first negative electrode active material layer to the thickness of the second negative electrode active material layer may be 1:9-9:1, for example, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1.
  • the thinner the first negative electrode active material layer and the thicker the second negative electrode active material layer the stronger the lithium intercalation capability of the negative electrode, that is, the battery charging kinetics is enhanced, and the risk of lithium evolution during high-rate charging is reduced.
  • the ratio of the thickness of the first negative electrode active material layer to the thickness of the second negative electrode active material layer is 5:5, and the mass ratio of the first silicon material in the first negative electrode active material layer is 3. %, 5%, 7% or 9%, the mass proportion of the second silicon material in the second negative electrode active material layer is 0%, 1%, 2% or 3%, the first silicon material and the The sum of the mass of the second silicon material accounts for 1.5%, 3%, 4.5% or 6% of the total mass of the first negative electrode active material layer and the second negative electrode active material layer.
  • the ratio of the thickness of the first negative electrode active material layer to the thickness of the second negative electrode active material layer is 8:2, and the mass ratio of the first silicon material in the first negative electrode active material layer is 3. %, 5%, 7% or 9%, the mass ratio of the second silicon material in the second negative electrode active material layer is 0%, 1%, 2% or 3%, the first silicon material and the The sum of the mass of the second silicon material accounts for 2.4%, 4.2%, 6% or 7.8% of the total mass of the first negative electrode active material layer and the second negative electrode active material layer.
  • the thickness of the first negative electrode active material layer is 20-180 ⁇ m, preferably 20-150 ⁇ m, such as 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m , 140 ⁇ m, 150 ⁇ m;
  • the thickness of the second negative electrode active material layer is 20-180 ⁇ m, preferably 50-180 ⁇ m, such as 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 140 ⁇ m, 150 ⁇ m, 160 ⁇ m, 170 ⁇ m, 180 ⁇ m.
  • the first silicon material and/or the second silicon material may be selected from one or more of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, and silicon alloys.
  • the first silicon material and/or the second silicon material is subjected to a coating treatment, and the coating comprises a carbon material or at least one of Al, Si, Ti, Mn, V, Cr, Co or Zr oxide.
  • the coating mentioned in this application is that coating treatment is performed on at least part of the surface of the silicon material.
  • the median particle size D50 is 0.01-1 ⁇ m, and the thickness of the carbon coating layer is 1-10 nm .
  • the median particle size D50 is 1-10 ⁇ m.
  • the molecular formula of the silicon oxide compound is SiO x , wherein 0.5 ⁇ x ⁇ 1.5.
  • the OI value of the first graphite is 5-7
  • the OI value of the second graphite is 3-5
  • the OI value of the first graphite is greater than the OI value of the second graphite.
  • the ultimate compaction density of the first graphite is greater than or equal to the ultimate compaction density of the second graphite, wherein the ultimate compaction density means that the graphite particles are not crushed, and the lithium-deintercalation ability is not affected.
  • the maximum compaction density under the influence premise is not limited to the maximum compaction density under the influence premise.
  • the ultimate compacted density of the first graphite is 1.75-1.83 g/cm 3 ; the ultimate compacted density of the second graphite is 1.65-1.75 g/cm 3 .
  • the median particle size D50 of the first graphite is 10-20 ⁇ m; the median particle size D50 of the second graphite is 10-20 ⁇ m.
  • the second graphite surface is coated with hard carbon, and the thickness of the hard carbon coating layer is 5-20 nm.
  • the first graphite and the second graphite are the same or different, and are independently selected from at least one of artificial graphite, natural graphite, and the like.
  • the first negative electrode active material layer further includes a first conductive agent, a first dispersant and a first binder
  • the second negative electrode active material layer further includes a second conductive agent, a second dispersant and second binder.
  • first conductive agent and the second conductive agent are the same or different
  • first dispersant and the second dispersant are the same or different
  • first binder and the second binder are the same or different.
  • the mass percentage of each component in the first negative electrode active material layer is:
  • the mass percentage content of the first conductive agent is 0.01wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%; the mass percentage content of the first binder is 0.5wt% , 1wt%, 2wt%, 4wt%, 5wt%, the mass percentage of the first dispersant is 0.5wt%, 1wt%, 1.5wt%, 2.5wt%, 3wt%, the first negative electrode active material
  • the mass percentages are 98.99wt%, 97.5wt%, 95.5wt%, 92wt%, 90wt%.
  • the mass percentage of each component in the second negative electrode active material layer is:
  • the mass percentage content of the second conductive agent is 0.01wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%; the mass percentage content of the second binder is 0.5wt% %, 1wt%, 2wt%, 4wt%, 5wt%, the mass percentage of the second dispersant is 0.5wt%, 1wt%, 1.5wt%, 2.5wt%, 3wt%, the second negative electrode active
  • the mass percentage of the substance is 98.99wt%, 97.5wt%, 95.5wt%, 92wt%, 90wt%.
  • the first conductive agent and the second conductive agent are the same or different, and are independently selected from at least conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber. A sort of.
  • first binder and the second binder are the same or different, and are independently selected from styrene-butadiene rubber (SBR), polyacrylic acid, polyurethane, polyvinyl alcohol, polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PVDF). At least one of ethylene-fluorinated olefin copolymers.
  • SBR styrene-butadiene rubber
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • the first dispersant and the second dispersant are the same or different, and are independently selected from at least one of sodium carboxymethyl cellulose (CMC-Na) and lithium carboxymethyl cellulose (CMC-Li). .
  • the present application also provides a method for preparing the above-mentioned negative pole piece, the method comprising the following steps:
  • step 1) includes the following steps:
  • step 2) includes the following steps:
  • the present application also provides a lithium ion battery, the lithium ion battery comprising the above-mentioned negative pole piece.
  • the lithium ion battery further includes a positive electrode, an electrolyte, a separator, and an aluminum-plastic film.
  • the positive active material in the positive electrode sheet is lithium cobalt oxide.
  • the negative electrode pole piece of the present application can further improve the negative electrode doping without losing the cycle performance.
  • the amount of silicon increase the gram capacity of the negative electrode), so as to achieve the purpose of improving the energy density of the battery;
  • the negative electrode pole piece of the present application can improve the cycle performance of the battery without losing energy density.
  • FIG. 1 is a schematic structural diagram of a negative electrode piece of the present application.
  • A represents the negative electrode current collector
  • B represents the first negative electrode active material layer
  • C represents the second negative electrode active material layer.
  • the OI values of the first graphite and the second graphite used in the following examples were obtained by X-ray diffraction (XRD).
  • the ultimate compaction densities of the first graphite and the second graphite used in the following examples are by preparing negative electrode sheets of different compaction densities, shooting SEM to observe the particle integrity after rolling these pole pieces, and assembling the battery to test the performance. method is determined.
  • the second conductive agent conductive carbon black and carbon nanotubes with a mass ratio of 1:1
  • the second binder styrene-butadiene rubber
  • the second dispersant CMC-Na
  • the compaction density can adopt the ultimate compaction density of larger graphite, at this time, graphite particles with smaller ultimate compaction density will not be damaged), cut, and tableted to prepare a negative pole piece.
  • the thickness of the first negative electrode active material layer (one side) and the second negative electrode active material layer (one side) in the negative electrode pole piece are both 90 ⁇ m; the proportion of silicon material blending in the entire negative electrode active material is 5wt% .
  • the positive active material lithium cobalt oxide
  • the conductive agent conductive carbon black
  • the binder PVDF
  • the positive active material lithium cobalt oxide
  • the conductive agent conductive carbon black
  • the binder PVDF
  • the positive electrode slurry is coated on the positive electrode current collector (double-sided coating), dried, rolled, cut, and filmed to prepare a positive electrode pole piece.
  • the negative pole piece obtained in the first step, the positive pole piece and the separator obtained in the second step are wound into a roll core, and then packaged together with an aluminum plastic film to make a battery, and then liquid injection, aging, chemical formation, etc. are carried out. Secondary packaging, sorting and other processes, and finally the energy density and cycle performance of the battery are tested.
  • the preparation environment temperature of the electrode material should be kept at 20-30°C, and the humidity should be ⁇ 40% RH.
  • the equipment used in the preparation of the electrode material includes: mixer, coater, roller press, slitter, tablet machine, ultrasonic spot welding machine, top and side sealing machine, inkjet printer, film sticker, liquid injection machine , Forming cabinets, cold presses, sorting cabinets, vacuum ovens, etc.
  • the preparation of the lithium ion batteries of Examples 2-9 and Comparative Examples 1-5 is the same as that of Example 1, and the difference is only in the choice of graphite, the feeding ratio of each component in the negative electrode slurry, and the coating structure. See Table 1; wherein, in the negative electrode pieces of Comparative Examples 2-4, only one layer of slurry is coated on the surface of the negative electrode current collector, and the thickness of the negative electrode active material layer formed by the slurry is 180 ⁇ m, and other embodiments The surface of the negative electrode collector side of the negative electrode sheet and the comparative example is coated with two layers of slurry, and the sum of the thicknesses of the two negative electrode active material layers formed by the two layers of slurry is 180 ⁇ m.
  • the preparation method of the lithium ion battery in Example 10 is basically the same as that in Example 1, and the difference in Example 10 is only in that the first silicon material and the second silicon material are different from those in Example 1, and the first silicon material and the second silicon material in Example 10 are different.
  • the difference between Examples 11-12 is that the thickness of the hard carbon coating of the second graphite material is different from The thickness of the hard carbon coating layer of the second graphite material of Example 11 was 15 nm, and the thickness of the second graphite coating layer of Example 12 was 20 nm.
  • the cycle performance of the battery was tested by the blue electric test cabinet.
  • the battery was charged and discharged at a rate of 0.7C/0.5C in the voltage range of 4.45V-2.75V at 25°C.
  • a 600g PPG thickness gauge was used to test the initial half of the battery. Electric (3.87V) thickness, and then measure the fully charged thickness of the battery every 50 cycles.
  • Capacity retention rate (%) current cycle number discharge capacity (mAh)/first discharge capacity (mAh)*100%.
  • Battery thickness swelling rate (%) current cycle number battery thickness (mm)/initial thickness (mm)*100%.
  • Example 1-3 when the proportion of silicon-oxygen material in the negative electrode slurry A to the total mass of the first negative electrode active material layer is 1-9wt% When it decreases gradually, the energy density of the battery decreases by about 3Wh/L for every 2wt% decrease, and the cycle capacity retention rate increases by about 1%.
  • the proportion of silicon oxide material in the negative electrode slurry A in Example 6 to the total mass of the first negative electrode active material layer is 12wt%, and the energy density of the battery is increased by 6Wh/L compared with Example 1, but the capacity retention rate drops sharply 12%; the negative electrode slurry A in Comparative Example 1 has no silicon-oxygen material, although the capacity retention rate is increased by 4%, but the energy density of the battery decreases by 12Wh/L.
  • Example 1 and Example 4 Comparing Example 1, Example 4, Example 7 and Example 9 in the above table, it can be seen that in Example 1 and Example 4, when the ratio of the silicon-oxygen material in the negative electrode slurry B to the total mass of the second negative electrode active material layer is When varying between 1-3 wt%, the energy density and cycle capacity retention of the battery were negatively correlated and slightly changed.
  • the proportion of silicon-oxygen material in the negative electrode slurry B in Example 7 to the total mass of the second negative electrode active material layer is 5wt%, the energy density of the battery is increased by 5Wh/L compared with Example 1, but the capacity retention rate drops sharply 7%; the negative electrode slurry B in Example 9 has no silicon oxide material, although the energy density is reduced by 3Wh/L compared with Example 1, but the capacity retention rate is increased by 2%.
  • Example 5 Compared with Example 1, Example 5 and Example 8 in the above table, when the ultimate compaction density of the first graphite is increased to 1.83 g/cm 3 , the overall compaction of the negative pole piece can be increased to 1.83 g/cm 3 , so the implementation The energy density of Example 5 is 7Wh/L higher than that of Example 1, and because of the higher OI value of the graphite, the capacity retention rate is decreased by 2%.
  • the ultimate compaction density of the first graphite in Example 8 is reduced to 1.58 g/cm 3
  • the overall compaction of the negative pole piece is reduced to 1.7 g/cm 3 of the second graphite, and the capacity retention rate of Example 8 is higher than that of Example 8. 1 is 3% higher, but the energy density is 20 Wh/L lower than that of Example 1.
  • Example 1 Comparing Example 1 with Comparative Example 2, the amount of silicon and oxygen in the negative electrode sheets of the two is the same, accounting for 5wt% of the negative electrode active material, and the energy density of the battery is the same, but the negative electrode monolayer coating structure of Comparative Example 3 is the same. , the battery cycle capacity retention rate was 6% lower than that of Example 1.
  • Comparing Example 1 with Comparative Example 3 Comparative Example 4 is equivalent to a single-layer coating structure with only slurry B coated, a negative compaction density of 1.7 g/cm 3 , and a silicon-oxygen content of 2%. Although its capacity retention at 400 cycles was 4.5% higher than that of Example 1, the energy density was reduced by 29 Wh/L.
  • Comparing Example 1 with Comparative Example 4 Comparative Example 5 is equivalent to a single-layer coating structure with only slurry A coating, a negative compaction density of 1.8 g/cm 3 , and a silicon-oxygen content of 8%. Although its energy density was 9 Wh/L higher than that of Example 1, the capacity retention rate at 400 cycles decreased by 10%.
  • Comparing Example 1 with Comparative Example 5 Comparative Example 5 is equivalent to exchanging the positions of the first active material layer and the second active material layer of Example 1, the energy density remains unchanged, but the capacity retention rate at 400 cycles decreases by 4. %.
  • Example 10 uses carbon-coated elemental silicon. Although the energy density is increased by 2Wh/L, the capacity retention rate at 400 cycles is decreased by 3%, and the thickness expansion rate of the battery at 400 cycles is increased. 1%.
  • Example 11-12 Comparing Example 11-12 with Example 1, the increase in the thickness of the hard carbon coating layer of the second graphite in Example 11-12 will lead to a decrease in the first coulombic efficiency of the second graphite material, and the greater the coating amount, the higher the coulombic efficiency. The more the efficiency drops, the energy density of Examples 11-12 is lower than that of Example 1, but the cycle retention is improved compared to Example 1.

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Abstract

本申请提供一种掺硅负极极片及包括该负极极片的锂离子电池。本申请通过双层涂布设备，在负极集流体两侧分别涂覆两层组成不同的第一负极活性物质层和第二负极活性物质层，其中，第一负极活性物质层中包括第一石墨和第一硅材料，第二负极活性物质层中包括第二石墨能够使包含该负极极片的电芯具有更高的能量密度和循环性能。另一方面，两层浆料分别使用OI值(OI＝I 004/I 110，其中，I 004为石墨在X射线衍射时004晶面的峰强度，I 110为石墨在X射线衍射时110晶面的峰强度)不同的石墨材料，紧贴负极集流体的第一负极活性物质层的第一石墨的OI值大于远离负极集流体的第二负极活性物质层的第二石墨的OI值，这种设计能够有效提高负极的充电能力，进一步优化电芯的循环性能。

Description

一种掺硅负极极片及包括该负极极片的锂离子电池
本申请要求于2020年07月16日提交中国专利局、申请号为202010688051.3、申请名称为“一种掺硅负极极片及包括该负极极片的锂离子电池”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
本申请属于锂离子电池技术领域，具体涉及一种掺硅负极极片及包括该负极极片的锂离子电池。
背景技术
随着人们对手机、笔记本电脑等电子产品性能要求的逐步提高，锂离子电池的快速发展显得尤为重要。提高电池的能量密度，同时不损失循环性能，一直是锂电工作者们努力的目标。
在现有的锂离子电池负极涂布结构中，一般采用单层涂布结构，该结构的特点是涂料层各处分布均匀，但是也存在一定问题，由于在硅材料中锂的固相扩散速度比石墨低，即硅材料的嵌锂速度比石墨的要慢，导致在引入硅材料，负极容易发生充电析锂的问题。因此，提出一种既具有更高负极克容量，又不会恶化负极充电性能的掺硅负极片显得尤为重要。
发明内容
为了提高电芯的能量密度，使用高克容量的硅材料与石墨掺混作为负极主材是一种有效的解决方法。但由于硅材料的固有性质，随着其掺混量的提高，电芯循环性能急剧恶化，循环过程的膨胀率迅速增大，这一直是亟待解决的行业难题。
基于以上现象，本申请通过双层涂布设备，在负极集流体两侧分别涂覆两层组成不同的第一负极活性物质层和第二负极活性物质层， 其中，第一负极活性物质层中包括第一石墨和第一硅材料，第二负极活性物质层中包括第二石墨能够使包含该负极极片的电芯具有更高的能量密度和循环性能。另一方面，两层浆料分别使用OI值(OI＝I 004/I 110，其中，I 004为石墨在X射线衍射时004晶面的峰强度，I 110为石墨在X射线衍射时110晶面的峰强度)不同的石墨材料，紧贴负极集流体的第一负极活性物质层的第一石墨的OI值大于远离负极集流体的第二负极活性物质层的第二石墨的OI值，这种设计能够有效提高负极的充电能力，进一步优化电芯的循环性能。
本申请目的是通过如下技术方案实现的：
一种负极极片，所述负极极片包括负极集流体、第一负极活性物质层和第二负极活性物质层，所述第一负极活性物质层设置在负极集流体表面，所述第二负极活性物质层设置在所述第一负极活性物质层表面；
其中，所述第一负极活性物质层包括第一负极活性物质，所述第一负极活性物质包括第一石墨和第一硅材料；
所述第二负极活性物质层包括第二负极活性物质，所述第二负极活性物质包括第二石墨；
所述第一石墨的OI值大于所述第二石墨的OI值；OI＝I 004/I 110，其中，I 004为石墨在X射线衍射时004晶面的峰强度，I 110为石墨在X射线衍射时110晶面的峰强度)所述OI值表示石墨的取向指数，石墨OI值越小越有利于锂离子的扩散，同时其极限压实密度会降低。
本申请中远离集流体的负极浆料采用OI值较小的石墨，能够有效增强锂离子的扩散能力，提高负极的充电性能。靠近集流体的负极浆料采用OI值较大的石墨，能够提升负极片的压实密度，从而提升电池的能量密度。
根据本申请，所述第二负极活性材料还包括第二硅材料；所述第一硅材料在第一负极活性物质层的质量占比大于所述第二硅材料在第二负极活性物质层的质量占比。
进一步地，在一种具体的实施方式中，所述第一硅材料在第一负极活性物质层的质量占比为3-9wt％，所述第二硅材料在第二负极活 性物质层的质量占比为1-3wt％。
在另一种具体的实施方式中，所述第一硅材料在第一活性物质层的质量占比为3-9wt％，所述第二硅材料在第二负极材料物质层中的质量占比为0。
在以上两种具体的实施方式中，由于硅材料在脱嵌锂离子过程中的体积变化大，故增加其掺入量时，会导致循环过程中发生更多的颗粒破裂，引起粘接和导电失效，负极SEI不断生长，消耗锂离子和电解液，负极片增厚、活性物质脱落。宏观表现为电池的容量保持率衰减快和厚度膨胀率增长快。所述第一硅材料的质量占比较高可以提高电池的能量密度；所述第二硅材料的质量占比较低可以保证负极片第二负极活性物质层的充电和循环性能，进而提高整个电池的循环性能。
根据本申请，所述第一硅材料和所述第二硅材料的质量之和占所述第一负极活性物质层和所述第二负极活性物质层总质量的1-9wt％。
根据本申请，所述第一负极活性物质层的厚度与所述第二负极活性物质层的厚度比可以为1:9-9:1，例如为1:9、2:8、3:7、4:6、5:5、6:4、7:3、8:2、9:1。所述第一负极活性物质层越薄、第二负极活性物质层越厚，负极嵌锂能力越强，即电池充电动力学增强，大倍率充电析锂风险降低。
示例性地，所述第一负极活性物质层的厚度与所述第二负极活性物质层的厚度比为5:5，所述第一硅材料在第一负极活性物质层的质量占比为3％、5％、7％或9％，所述第二硅材料在第二负极活性物质层的质量占比为0％，1％、2％或3％，所述第一硅材料和所述第二硅材料的质量之和占所述第一负极活性物质层和所述第二负极活性物质层总质量为1.5％、3％、4.5％或6％。
示例性地，所述第一负极活性物质层的厚度与所述第二负极活性物质层的厚度比为8:2，所述第一硅材料在第一负极活性物质层的质量占比为3％、5％、7％或9％，所述第二硅材料在第二负极活性物质层的质量占比为0％、1％、2％或3％，所述第一硅材料和所述第二硅材料的质量之和占所述第一负极活性物质层和所述第二负极活性物质层总质量2.4％、4.2％、6％或7.8％。
根据本申请，所述第一负极活性物质层的厚度为20-180μm，优选为20-150μm，例如为20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μm、110μm、120μm、130μm、140μm、150μm；所述第二负极活性物质层的厚度为20-180μm，优选为50-180μm，例如为50μm、60μm、70μm、80μm、90μm、100μm、110μm、120μm、130μm、140μm、150μm、160μm、170μm、180μm。
所述第一硅材料和/或第二硅材料可选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或几种。
优选的，对所述第一硅材料和/或第二硅材料进行包覆处理，包覆物包括碳材料或Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种的氧化物。需要说明的是，本申请中所提及的包覆均是在硅材料的至少部分表面进行包覆处理。
根据本申请，所述第一硅材料和/或所述第二硅材料为碳包覆的单质硅时，其中值粒径D50为0.01-1μm，所述碳包覆层的厚度为1-10nm。
根据本申请，所述第一硅材料和/或第二硅材料为硅氧化合物时，其中值粒径D50为1-10μm。
进一步地，硅氧化合物的分子式为SiO x，其中，0.5≤x≤1.5。
根据本申请，所述第一石墨的OI值为5-7，所述第二石墨的OI值为3-5，且所述第一石墨的OI值大于所述第二石墨的OI值。
根据本申请，所述第一石墨的极限压实密度大于等于所述第二石墨的极限压实密度，其中，所述极限压实密度是指石墨颗粒不被压破、脱嵌锂能力不受影响前提下的最大压实密度。
根据本申请，所述第一石墨的极限压实密度为1.75-1.83g/cm 3；所述第二石墨的极限压实密度为1.65-1.75g/cm 3。
根据本申请，所述第一石墨的中值粒径D50为10-20μm；所述第二石墨的中值粒径D50为10-20μm。
根据本申请，所述第二石墨表面包覆有硬碳，硬碳包覆层的厚度5-20nm。
根据本申请，所述第一石墨和所述第二石墨相同或不同，彼此独 立地选自人造石墨、天然石墨等中的至少一种。
根据本申请，所述第一负极活性物质层还包括第一导电剂、第一分散剂和第一粘结剂，所述第二负极活性物质层还包括第二导电剂、第二分散剂和第二粘结剂。
其中，所述第一导电剂和第二导电剂相同或不同、第一分散剂和第二分散剂相同或不同、第一粘结剂和第二粘结剂相同或不同。
根据本申请，所述第一负极活性物质层中各组分的质量百分含量为：
90-98.99wt％的第一负极活性物质、0.01-2wt％的第一导电剂、0.5-3wt％的第一分散剂、0.5-5wt％的第一粘结剂。
示例性地，所述第一导电剂的质量百分含量为0.01wt％、0.5wt％、1wt％、1.5wt％、2wt％；所述第一粘结剂的质量百分含量为0.5wt％、1wt％、2wt％、4wt％、5wt％，所述第一分散剂的质量百分含量为0.5wt％、1wt％、1.5wt％、2.5wt％、3wt％，所述第一负极活性物质的质量百分含量为98.99wt％、97.5wt％、95.5wt％、92wt％、90wt％。
根据本申请，所述第二负极活性物质层中各组分的质量百分含量为：
90-98.99wt％的第二负极活性物质、0.01-2wt％的第二导电剂、0.5-3wt％的第二分散剂、0.5-5wt％的第二粘结剂。
示例性地，所述第二导电剂的质量百分含量为0.01w t％、0.5wt％、1wt％、1.5wt％、2wt％；所述第二粘结剂的质量百分含量为0.5wt％、1wt％、2wt％、4wt％、5wt％，所述第二分散剂的质量百分含量为0.5wt％、1wt％、1.5wt％、2.5wt％、3wt％，所述第二负极活性物质的质量百分含量为98.99wt％、97.5wt％、95.5wt％、92wt％、90wt％。
其中，所述第一导电剂和第二导电剂相同或不同，彼此独立地选自导电炭黑、乙炔黑、科琴黑、导电石墨、导电碳纤维、碳纳米管、金属粉、碳纤维中的至少一种。
其中，所述第一粘结剂和第二粘结剂相同或不同，彼此独立地选自丁苯橡胶(SBR)、聚丙烯酸、聚氨酯、聚乙烯醇、聚偏氟乙烯(PVDF)、偏氟乙烯-氟化烯烃的共聚物中的至少一种。
其中，所述第一分散剂和第二分散剂相同或不同，彼此独立地选自羧甲基纤维素钠(CMC-Na)、羧甲基纤维素锂(CMC-Li)中的至少一种。
本申请还提供上述负极极片的制备方法，所述方法包括如下步骤：
1)分别配制形成第一负极活性物质层的浆料和形成第二负极活性物质层的浆料；
2)使用双层涂布机，将形成第一负极活性物质层的浆料和形成第二负极活性物质层的浆料涂覆在负极集流体表面，制备得到所述负极极片。
示例性地，步骤1)包括如下步骤：
(1-1)将第一石墨与第一硅材料掺混，加入一定比例的第一导电剂、第一粘结剂、第一分散剂，然后用水调节制成适当固含量的负极浆料A；
(1-2)将第二石墨与第二硅材料(若无第二硅材料可省去)掺混，加入一定比例的第二导电剂、第二粘结剂、第二分散剂，然后用水调节制成适当固含量的负极浆料B。
示例性地，步骤2)包括如下步骤：
使用双层涂布机，将负极浆料A涂覆在负极集流体上，烘干，将负极浆料B涂覆在负极浆料A上，烘干、辊压、分切、制片，制备得到所述负极极片。
本申请还提供一种锂离子电池，所述锂离子电池包括上述负极极片。
根据本申请，所述锂离子电池还包括正极极片、电解液、隔膜、以及铝塑膜。
根据本申请，所述正极极片中的正极活性物质为钴酸锂。
本申请的有益效果：
(1)与现有的底层采用掺硅负极、顶层和底层都含有石墨负极的负极双层涂布结构相比，本申请的负极极片能够在不损失循环性能的前提下，进一步提高负极掺硅量(提高负极克容量)，以此达到提高电池能量密度的目的；
(2)与同比例硅掺混量的负极单层涂布常规结构相比，本申请的负极极片能够在不损失能量密度的前提下，提高电池的循环性能。
附图说明
图1为本申请的负极极片结构示意图。
其中，A代表负极集流体，B代表第一负极活性物质层，C为第二负极活性物质层。
具体实施方式
下文将结合具体实施例对本申请做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
在本申请的描述中，需要说明的是，术语“第一”、“第二”等仅用于描述目的，而并非指示或暗示相对重要性。
下述实施例中所使用的第一石墨和第二石墨的OI值是采用X射线衍射(XRD)测试得到的。
下述实施例中所使用的第一石墨和第二石墨的极限压实密度是通过制备不同压实密度的负极片，将这些极片辊压后拍摄SEM观察颗粒完整度，并组装电池测试性能的方法确定。
实施例1
(1)负极片的制备
(1-1)第一负极活性物质浆料(记为负极浆料A)的制备
将第一石墨(人造石墨，OI值为5.8，极限压实密度为1.8g/cm 3，D50为14.6μm)、第一硅材料(硅氧化物，SiO x，x＝1，D50为6.2μm)、 第一导电剂(质量比1:1的导电炭黑和碳纳米管)、第一粘结剂(丁苯橡胶)和第一分散剂(CMC-Na)按88:8:1:1:2的质量比混合，然后加入水搅拌制成负极浆料A；
(1-2)第二负极活性物质浆料(记为负极浆料B)的制备
将第二石墨(人造石墨，OI值为3.5，极限压实密度为1.7g/cm 3，D50为15.2μm，硬碳包覆层厚度为5nm)、第二硅材料(硅氧化物，SiO x，x＝1，D50为6.2μm)、第二导电剂(质量比1:1的导电炭黑和碳纳米管)、第二粘结剂(丁苯橡胶)和第二分散剂(CMC-Na)按95:2:0.5:1:1.5的质量比混合，然后加入水搅拌制成负极浆料B。
(1-3)然后通过双层涂布设备把负极浆料A和负极浆料B按5:5的质量比一次涂布在负极集流体上(双面涂布)，烘干、辊压(压实密度为p＝1.8g/cm 3。实验表明，采用负极双层涂布结构时，若第一石墨与第二石墨的极限压实密度差距不超过0.15g/cm 3，则负极片辊压压实密度可以采用较大石墨的极限压实密度，此时极限压实密度较小的石墨颗粒不会被破坏)、分切、制片，制备得到负极极片。所述负极极片中第一负极活性物质层(单侧)和第二负极活性物质层(单侧)的厚度均为90μm；硅材料掺混量在整个负极活性物质中的占比为5wt％。
(2)正极片的制备
将正极活性物质(钴酸锂)、导电剂(导电炭黑)、粘结剂(PVDF)按7.8:1.1:1.1的质量比混合，然后加入的N-甲基吡咯烷酮搅拌分散制成正极浆料；然后把正极浆料涂布在正极集流体上(双面涂布)，烘干、辊压、分切、制片，制备得到正极极片。
(3)电池的制备
将第一步制得的负极极片与第二步制得的正极极片与隔膜卷绕制成卷芯，再与铝塑膜一起封装制成电池，然后进行注液、陈化、化成、二次封装、分选等工序，最后对电池的能量密度和循环性能进行测试。
所述电极材料的制备环境温度应保持在20～30℃，湿度≤40％RH。
所述电极材料的制备用到的设备包括：搅拌机、涂布机、辊压机、分切机、制片机、超声波点焊机、顶侧封机、喷码机、贴膜机、注液 机、化成柜、冷压机、分选柜、真空烘箱等。
实施例2-9和对比例1-5
实施例2-9和对比例1-5的锂离子电池的制备同实施例1，区别仅在于石墨的选择不同、负极浆料中各组分的投料比不同、以及涂覆的结构不同，具体参见表1所示；其中，对比例2-4的负极极片中负极集流体一侧表面仅涂覆一层浆料，所述浆料形成的负极活性物质层的厚度为180μm，其他实施例和对比例的负极极片中负极集流体一侧表面均为涂覆两层浆料，所述两层浆料形成的两层负极活性物质层的厚度之和为180μm。
实施例10-12
实施例10的锂离子电池的制备方法与实施例1基本一致，其中实施例10的区别仅在于第一硅材料和第二硅材料与实施例1不同，实施例10的第一硅材料和第二硅材料均为碳包覆的单质硅(D50＝100nm，碳包覆层厚度5nm)，实施例11-12的区别仅在于第二石墨材料的硬碳包覆厚度与实施例1不同，实施例11的第二石墨材料的硬碳包覆层厚度为15nm，实施例12的第二石墨包覆层厚度为20nm。
对上述实施例和对比例的电池进行性能测试和能量密度测试，测试过程如下：
1)能量密度测试：
将制作完成的电池用600g PPG测厚仪测试电池的厚度(单位mm)，以电池的型号确定长度和宽度(单位mm)，并视为固定值。能量密度(Energy Density，ED，单位Wh/L)＝分选放电能量值(Wh)/电池厚度/电池长度/电池宽度*1000。
2)循环性能测试和电池厚度膨胀率测试：
采用蓝电测试柜测试电池的循环性能，25℃下在4.45V-2.75V电压范围内以0.7C/0.5C倍率对电池进行充放电循环，循环前用600g PPG测厚仪测试电池的初始半电(3.87V)厚度，之后每循环50次测一次 电池的满电厚度。
容量保持率(％)＝当前循环次数放电容量(mAh)/首次放电容量(mAh)*100％。
电池厚度膨胀率(％)＝当前循环次数电池厚度(mm)/初始厚度(mm)*100％。
测试结果如表2所示。
表1
Figure PCTCN2021105841-appb-000001
Figure PCTCN2021105841-appb-000002
表2
  能量密度(Wh/L) 400圈容量保持率 400圈电池厚度膨胀率
实施例1 780 92％ 8％
实施例2 777 93％ 7.5％
实施例3 774 94％ 6.9％
实施例4 782 90％ 8.6％
实施例5 787 90％ 8.2％
实施例6 786 80％ 10.3％
实施例7 785 85％ 9.9％
实施例8 760 95％ 7.1％
实施例9 777 92％ 7.6％
实施例10 782 89％ 9％
实施例11 777 93％ 8％
实施例12 770 94％ 8％
对比例1 768 96％ 4.2％
对比例2 780 86％ 10％
对比例3 751 96.5％ 4.9％
对比例4 789 82％ 9.5％
对比例5 780 88％ 8.6％
对比上表实施例1-3和对比例1、实施例6可知，实施例1-3中，当负极浆料A中硅氧材料占第一负极活性物质层总质量的比例在1-9wt％之间且逐渐减少时，每减少2wt％，电池的能量密度约减小3Wh/L，循环容量保持率约上升1％。实施例6中的负极浆料A中硅氧材料占第一负极活性物质层总质量的比例为12wt％，电池的能量密度相比实施例1提高了6Wh/L，只是容量保持率骤降了12％；对比例1中的负极浆 料A中无硅氧材料，虽然容量保持率提高了4％，但电池的能量密度下降了12Wh/L。
对比上表实施例1、实施例4、实施例7和实施例9可知，实施例1和实施例4中，当负极浆料B中硅氧材料占第二负极活性物质层总质量的比例在1-3wt％之间变化时，电池的能量密度和循环容量保持率呈负相关稍有变化。实施例7中的负极浆料B中硅氧材料占第二负极活性物质层总质量的比例为5wt％，电池的能量密度相比实施例1提高了5Wh/L，只是容量保持率骤降了7％；实施例9中的负极浆料B中无硅氧材料，能量密度相比实施例1虽然下降了3Wh/L，但容量保持率提升了2％。
对比上表实施例1、实施例5和实施例8，当第一石墨的极限压实密度提高至1.83g/cm 3时，负极极片整体压实可提高至1.83g/cm 3，故实施例5的能量密度比实施例1的能量密度提高了7Wh/L，又因为该石墨OI值较高，故容量保持率下降了2％。实施例8中的第一石墨的极限压实密度降低至1.58g/cm 3时，负极极片整体压实降低至第二石墨的1.7g/cm 3，实施例8的容量保持率比实施例1提高了3％，但是能量密度比实施例1的能量密度降低了20Wh/L。
将实施例1与对比例2相比，二者负极片的硅氧掺混量相同，都占负极活性物质的5wt％，电池的能量密度相同，但在对比例3的负极单层涂布结构中，电池循环容量保持率比实施例1低了6％。
将实施例1与对比例3相比，对比例4相当于仅涂覆浆料B，负极压实密度为1.7g/cm 3，硅氧掺混量为2％的单层涂布结构。虽然其400圈的容量保持率比实施例1高4.5％，但能量密度降低了29Wh/L。
将实施例1与对比例4相比，对比例5相当于仅涂覆浆料A，负极压实密度为1.8g/cm 3，硅氧掺混量为8％的单层涂布结构。虽然其能量密度比实施例1高9Wh/L，但400圈的容量保持率下降了10％。
将实施例1与对比例5相比，对比例5相当于将实施例1的第一活性物质层和第二活性物质层调换位置，能量密度不变，但400圈的容量保持率下降了4％。
将实施例1和实施例10对比，实施例10使用了碳包覆的单质硅， 虽然能量密度提升了2Wh/L，但是400圈容量保持率下降了3％，且400圈电池厚度膨胀率增加了1％。
将实施例11-12与实施例1对比，实施例11-12的第二石墨的硬碳包覆层厚度增加，会导致第二石墨材料的首次库伦效率下降，且包覆量越大，库伦效率下降越多，因此，实施例11-12的能量密度较实施例1低，但循环保持率相比实施例1有提高。
上文说明摘要整理出数个实施例的特征，这使得所属技术领域中具有通常知识者能够更加理解本申请的多种方面。所属技术领域中具有通常知识者可轻易地使用本申请作为基础，以设计或修改其他组合物，以便实现与此处申请的实施例相同的目的及/或达到相同的优点。所属技术领域中具有通常知识者亦可理解，这些均等的实例并未悖离本申请的精神与范畴，且其可对本申请进行各种改变、替换与修改，而不会悖离本申请的精神与范畴。虽然本文中所揭示的方法己参考以具体次序执行的具体操作加以描述，但应理解，可在不脱离本申请的教示的情况下组合、细分或重新排序这些操作以形成等效方法。因此，除非本文中特别指示，否则操作的次序及分组不是对本申请的限制。
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (22)

  1. 一种负极极片，所述负极极片包括负极集流体、第一负极活性物质层和第二负极活性物质层，所述第一负极活性物质层设置在负极集流体表面，所述第二负极活性物质层设置在所述第一负极活性物质层表面；
    其中，所述第一负极活性物质层包括第一负极活性物质，所述第一负极活性物质包括第一石墨和第一硅材料；
    所述第二负极活性物质层包括第二负极活性物质，所述第二负极活性物质包括第二石墨；
    所述第一石墨的OI值大于所述第二石墨的OI值；其中，OI＝I 004/I 110；I 004为石墨在X射线衍射时004晶面的峰强度，I 110为石墨在X射线衍射时110晶面的峰强度。
  2. 根据权利要求1所述的负极极片，其中，所述第二负极活性物质还包括第二硅材料；所述第一硅材料在第一负极活性物质层的质量占比大于所述第二硅材料在第二负极活性物质层的质量占比。
  3. 根据权利要求2所述的负极极片，其中，所述第一硅材料在第一负极活性物质层的质量占比为3-9wt％，所述第二硅材料在第二负极活性物质层的质量占比为1-3wt％。
  4. 根据权利要求2所述的负极极片，其中，所述第一硅材料在第一活性物质层的质量占比为3-9wt％，所述第二硅材料在第二负极材料物质层中的质量占比为0。
  5. 根据权利要求2-4任一项所述的负极极片，其中，所述第一硅材料和所述第二硅材料的质量之和占所述第一负极活性物质层和所述第二负极活性物质层总质量的1-9wt％。
  6. 根据权利要求1-5任一项所述的负极极片，其中，所述第一负极活性物质层的厚度与所述第二负极活性物质层的厚度比为1:9-9:1。
  7. 根据权利要求1-6任一项所述的负极极片，其中，所述第一负极活性物质层的厚度为20-180μm。
  8. 根据权利要求1-7任一项所述的负极极片，其中，所述第二负 极活性物质层的厚度为20-180μm。
  9. 根据权利要求1所述的负极极片，其中，所述第一石墨的OI值为5-7，所述第二石墨的OI值为3-5。
  10. 根据权利要求1-9任一项所述的负极极片，其中，所述第一硅材料选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或几种。
  11. 根据权利要求10所述的负极极片，其特征在于，对所述第一硅材料进行包覆处理，包覆物包括碳材料或Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种的氧化物。
  12. 根据权利要求11所述的负极极片，其特征在于，所述第一硅材料为碳包覆的单质硅，所述碳包覆的单质硅的中值粒径D50为0.01-1μm，碳包覆层的厚度为1-10nm。
  13. 根据根据权利要求2-5任一项所述的负极极片，其中，所述第二硅材料选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或几种。
  14. 根据权利要求13所述的负极极片，其中，对所述第二硅材料进行包覆处理，包覆物包括碳材料或Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种的氧化物。
  15. 根据权利要求14所述的负极极片，其中，所述第二硅材料为碳包覆的单质硅，所述碳包覆的单质硅的中值粒径D50为0.01-1μm，碳包覆层的厚度为1-10nm。
  16. 根据权利要求10或11所述的负极极片，其中，所述硅氧化合物的中值粒径D50为1-10μm。
  17. 根据权利要求1-16任一项所述的负极极片，其中，所述第一石墨的极限压实密度为1.75-1.83g/cm 3；所述第二石墨的极限压实密度为1.65-1.75g/cm 3。
  18. 根据权利要求1-17任一项所述的负极极片，其中，所述第一石墨的中值粒径D50为10-20μm，所述第二石墨的中值粒径D50为10-20μm。
  19. 根据权利要求1-18任一项所述的负极极片，其中，所述第二 石墨表面包覆有硬碳，硬碳包覆层的厚度为5-20nm。
  20. 根据权利要求1-19任一项所述的负极极片，其中，所述第一负极活性物质层还包括第一导电剂、第一分散剂和第一粘结剂；所述第一负极活性物质层中各组分的质量百分含量为：90-98.99wt％的第一负极活性物质、0.01-2wt％的第一导电剂、0.5-3wt％的第一分散剂、0.5-5wt％的第一粘结剂。
  21. 根据权利要求1-20任一项所述的负极极片，其中，所述第二负极活性物质层还包括第二导电剂、第二分散剂和第二粘结剂；所述第二负极活性物质层中各组分的质量百分含量为：90-98.99wt％的第二负极活性物质、0.01-2wt％的第二导电剂、0.5-3wt％的第二分散剂、0.5-5wt％的第二粘结剂。
  22. 一种锂离子电池，所述锂离子电池包括权利要求1-21任一项所述的负极极片。
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