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WO2020135110A1 - 负极活性材料、电池及装置 - Google Patents

负极活性材料、电池及装置 Download PDF

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Publication number
WO2020135110A1
WO2020135110A1 PCT/CN2019/125307 CN2019125307W WO2020135110A1 WO 2020135110 A1 WO2020135110 A1 WO 2020135110A1 CN 2019125307 W CN2019125307 W CN 2019125307W WO 2020135110 A1 WO2020135110 A1 WO 2020135110A1
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Prior art keywords
silicon oxide
negative electrode
active material
battery
electrode active
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PCT/CN2019/125307
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English (en)
French (fr)
Inventor
曾毓群
梁成都
赵玉珍
黄起森
官英杰
温严
Original Assignee
宁德时代新能源科技股份有限公司
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Publication of WO2020135110A1 publication Critical patent/WO2020135110A1/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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of batteries, and in particular to a negative electrode active material, battery, and device.
  • the thickness of the negative pole piece made of silicon as the negative electrode active material rebounds greatly during the use of the battery and the porosity of the negative pole piece is also high, so that the structure of the negative pole piece gradually changes from the initial dense state to loose and porous In the state, the conductive network of the negative pole piece is damaged, and the electrical contact between the negative electrode active materials is deteriorated, which seriously affects the cycle stability and cycle life of the battery.
  • the purpose of this application is to provide a negative electrode active material, a battery and a device.
  • This application can control the thickness rebound of the negative electrode sheet, ensure good electrical contact between the negative electrode active materials, and improve the battery Cycle stability and cycle life.
  • the present application provides a negative electrode active material, which includes a first silicon oxide and a second silicon oxide, wherein the particle size of the first silicon oxide is Dn10
  • the ratio of the particle diameter Dn10 of the second silicon oxide is 8-25
  • the particle diameter Dn10 of the first silicon oxide is 1.0 ⁇ m-5.0 ⁇ m
  • the particle diameter Dn10 of the second silicon oxide is 0.05 ⁇ m ⁇ 0.50 ⁇ m.
  • the present application provides a battery including the negative electrode active material according to the first aspect of the present application.
  • the present application provides an apparatus, which includes the battery described in the second aspect of the present application.
  • This application selects two kinds of silicon oxides with a specific Dn10 range to match to control the thickness rebound of the negative pole piece to ensure good electrical contact between the negative electrode active materials, thereby helping to improve the cycle stability and cycle life of the battery .
  • the device of the present application includes the aforementioned battery, and therefore has at least the same advantages as the aforementioned battery.
  • FIG. 1 is a schematic diagram of an embodiment of a battery.
  • FIG. 2 is a schematic diagram of an embodiment of a battery module.
  • FIG. 3 is a schematic diagram of an embodiment of a battery pack.
  • Fig. 4 is an exploded view of Fig. 3.
  • FIG. 5 is a schematic diagram of an embodiment of a device in which a battery is used as a power source.
  • the negative electrode active material, battery, and device according to the present application are described in detail below.
  • the negative electrode active material according to the first aspect of the present application includes a first silicon oxide and a second silicon oxide, wherein the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide Is 8-25, the particle size Dn10 of the first silicon oxide is 1.0 ⁇ m-5.0 ⁇ m, and the particle size Dn10 of the second silicon oxide is 0.05 ⁇ m-0.50 ⁇ m. It should be noted that Dn10 represents the particle size corresponding to the cumulative number percentage reaching 10%.
  • the particle size Dn10 of the first silicon oxide should not be too high, otherwise the content of fine particles in the negative electrode active material is too small, which is unfavorable for suppressing the thickness rebound of the negative electrode sheet.
  • the lower limit value of the particle size Dn10 of the first silicon oxide may be selected from 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m , 2.0 ⁇ m
  • the upper limit of the particle size Dn10 of the first silicon oxide can be selected from 5.0 ⁇ m, 4.8 ⁇ m, 4.5 ⁇ m, 4.2 ⁇ m, 4.0 ⁇ m, 3.8 ⁇ m, 3.6 ⁇ m, 3.4 ⁇ m, 3.2 ⁇ m, 3.0 ⁇ m, 2.8 ⁇ m, 2.6 ⁇ m, 2.4 ⁇ m, 2.0 ⁇ m.
  • the particle size Dn10 of the first silicon oxide is 1.7
  • the particle size Dn10 of the second silicon oxide should not be too small, otherwise the prepared negative pole piece will contain a large amount of fine particles, which may easily lead to increased consumption of electrolyte and deteriorate the cycle performance and service life of the battery.
  • the lower limit value of the particle size Dn10 of the second silicon oxide may be selected from 0.05 ⁇ m, 0.06 ⁇ m, 0.07 ⁇ m, 0.08 ⁇ m, 0.09 ⁇ m, 0.10 ⁇ m, 0.11 ⁇ m, 0.12 ⁇ m, 0.13 ⁇ m, 0.14 ⁇ m 0.15 ⁇ m
  • the upper limit of the particle size Dn10 of the second silicon oxide can be selected from 0.50 ⁇ m, 0.48 ⁇ m, 0.45 ⁇ m, 0.40 ⁇ m, 0.38 ⁇ m, 0.35 ⁇ m, 0.32 ⁇ m, 0.30 ⁇ m, 0.28 ⁇ m, 0.26 ⁇ m, 0.24 ⁇ m, 0.22 ⁇ m, 0.20 ⁇ m, 0.18 ⁇ m.
  • the particle size Dn10 of the second silicon oxide is 0.10 ⁇
  • the lower limit value of the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide may be selected from 8, 9, 10, 11, 12, 13, 14, 15, 16
  • the upper limit of the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide may be selected from 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15.
  • the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide is 10-20.
  • the negative electrode active material of the present application two kinds of silicon oxides with a specific Dn10 range are mixed and matched, which can effectively reduce the thickness rebound of the negative electrode piece and maintain good electrical contact between the negative electrode active materials, thereby helping In order to improve the cycle stability and cycle life of the battery.
  • the mixing and matching of the first silicon oxide and the second silicon oxide in different Dn10 ranges can greatly increase the compaction density of the negative electrode active material powder, and the compaction
  • the second silicon oxide with a smaller Dn10 has a smaller particle size and a larger number.
  • the thickness of the negative pole piece can be reduced Rebound and porosity, which can improve the cycle stability and cycle life of the battery.
  • the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide is too low, the quantity advantage of the second silicon oxide with a smaller Dn10 is almost lost, and it is difficult
  • the gap between a silicon oxide fills up, and the thickness of the negative pole piece rebounds greatly during the use of the battery.
  • the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide is too high, and the prepared negative pole piece will contain a large amount of fine particles, which easily leads to increased consumption of the electrolyte. Deteriorating the cycle performance and service life of the battery.
  • Dn10 represents the corresponding particle size when the cumulative number percentage reaches 10%, that is, the number of particles with a particle size smaller than the corresponding particle size of Dn10 accounts for 10% of the total number of all particles, which can more accurately and intuitively reflect the content of fine particles.
  • the volume particle size refers to the percentage of the total volume of particles whose particle size is less than a certain value to the total volume of all particles. For powders with a wide particle size distribution (such as negative electrode active materials), the volume percentage of fine particles in the negative electrode active material powder is negligible, but the fine particles of powder have a negative impact on the negative electrode active material powder (especially It is a silicon-containing negative electrode active material powder).
  • the volume expansion has a great influence, so the conventional volume particle size is used to characterize the content of fine particles in the negative electrode active material powder, and the quantitative particle size is used to characterize the negative electrode active material powder.
  • the content of fine particles in the material is more accurate and intuitive, which is beneficial to the reasonable control of the thickness rebound of the negative pole piece.
  • the particle diameter Dn10 of the negative electrode active material is 0.10 ⁇ m to 0.50 ⁇ m.
  • the lower limit value of the particle size Dn10 of the negative electrode active material may be selected from 0.10 ⁇ m, 0.11 ⁇ m, 0.12 ⁇ m, 0.13 ⁇ m, 0.14 ⁇ m, 0.15 ⁇ m, 0.16 ⁇ m, 0.17 ⁇ m, 0.18 ⁇ m, 0.19 ⁇ m, 0.20 ⁇ m
  • the upper limit of the particle size Dn10 of the negative electrode active material can be selected from 0.50 ⁇ m, 0.48 ⁇ m, 0.45 ⁇ m, 0.42 ⁇ m, 0.40 ⁇ m, 0.38 ⁇ m, 0.35 ⁇ m, 0.32 ⁇ m, 0.30 ⁇ m, 0.28 ⁇ m, 0.26 ⁇ m, 0.24 ⁇ m, 0.22 ⁇ m, 0.20 ⁇ m. More preferably, the particle size Dn10 of the negative electrode active material is 0.15 ⁇ m to 0.36
  • the thickness rebound and increase in porosity of the negative electrode sheet can be well controlled to maintain a good electrical charge between the negative electrode active materials Contact, on this basis, if the particle size distribution width of the two silicon oxides is further reasonably controlled, it is also helpful to improve the matching degree between the particles of the negative electrode active material and maintain a good electrode structure, which can further improve the cycle stability of the battery And cycle life.
  • the particle size distribution width is represented by (Dn90-Dn10)/Dn50.
  • Dn10, Dn50, and Dn90 represent the corresponding particle diameters when the cumulative number percentage reaches 10%, 50%, and 90%, respectively.
  • the first silicon oxide has a particle size distribution width of 0.8 to 1.2.
  • the lower limit of the particle size distribution width of the first silicon oxide may be selected from 0.80, 0.82, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96, 0.98, 1.00
  • the The upper limit of the particle size distribution width can be selected from 1.20, 1.18, 1.16, 1.14, 1.12, 1.10, 1.08, 1.06, 1.04, 1.02, 1.00.
  • the first silicon oxide has a particle size distribution width of 0.9 to 1.1.
  • the second silicon oxide has a particle size distribution width of 1.0-1.6.
  • the lower limit of the particle size distribution width of the second silicon oxide may be selected from 1.00, 1.02, 1.04, 1.06, 1.08, 1.10, 1.12, 1.14, 1.16, 1.18, 1.20, 1.22, 1.24, 1.26, 1.28, 1.30
  • the upper limit of the particle size distribution width of the second silicon oxide can be selected from 1.60, 1.58, 1.56, 1.54, 1.52, 1.50, 1.48, 1.46, 1.44, 1.42, 1.40, 1.38, 1.36, 1.34, 1.32, 1.30. More preferably, the second silicon oxide has a particle size distribution width of 1.1 to 1.5.
  • the negative electrode active material has a particle size distribution width of 1.0 to 1.5.
  • the lower limit of the particle size distribution width of the negative electrode active material may be selected from 1.00, 1.02, 1.04, 1.06, 1.08, 1.10, 1.12, 1.14, 1.16, 1.18, 1.20, 1.22, 1.25
  • the negative electrode active material The upper limit of the particle size distribution width can be selected from 1.50, 1.48, 1.46, 1.44, 1.42, 1.40, 1.38, 1.36, 1.34, 1.32, 1.30, 1.28, 1.25.
  • the negative electrode active material has a particle size distribution width of 1.1 to 1.4.
  • the thickness rebound and increase in porosity of the negative electrode sheet can be well controlled to maintain a good electrical charge between the negative electrode active materials Contact, on this basis, if the average volume particle size of the two silicon oxides is further reasonably controlled, it is also beneficial to promote the extraction and insertion of active ions in the negative electrode active material, which can further improve the cycle stability and cycle life of the battery .
  • the average volume particle diameter is represented by Dv50, and Dv50 represents the corresponding particle diameter when the cumulative volume percentage reaches 50%.
  • the ratio of the particle diameter Dv50 of the first silicon oxide to the particle diameter Dv50 of the second silicon oxide is 1.0-8.0.
  • the lower limit value of the ratio of the particle diameter Dv50 of the first silicon oxide to the particle diameter Dv50 of the second silicon oxide may be selected from 1.0, 1.1, 1.2, 1.3, 1.5, 1.6, 1.7, 1.8 , 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5
  • the upper limit of the ratio of the particle diameter Dv50 of the first silicon oxide to the particle diameter Dv50 of the second silicon oxide can be optionally selected from 8.0, 7.6, 7.2, 6.8, 6.4, 6.0, 5.6, 5.2, 4.8, 4.4, 4.0, 3.6, 3.2, 2.8, 2.4, 2.0.
  • the ratio of the particle diameter Dv50 of the first silicon oxide to the particle diameter Dv50 of the second silicon oxide is 1.5-7.2.
  • the particle diameter Dv50 of the first silicon oxide is 3.0 ⁇ m to 15.0 ⁇ m.
  • the lower limit value of the particle diameter Dv50 of the first silicon oxide may be selected from 3.0 ⁇ m, 3.2 ⁇ m, 3.4 ⁇ m, 3.6 ⁇ m, 3.8 ⁇ m, 4.0 ⁇ m, 4.2 ⁇ m, 4.4 ⁇ m, 4.6 ⁇ m, 4.8 ⁇ m , 5.0 ⁇ m, 5.2 ⁇ m, 5.4 ⁇ m, 5.6 ⁇ m, 5.8 ⁇ m, 6.0 ⁇ m
  • the upper limit of the particle size Dv50 of the first silicon oxide can be selected from 15.0 ⁇ m, 14.5 ⁇ m, 14.0 ⁇ m, 13.5 ⁇ m, 13.0 ⁇ m, 12.5 ⁇ m, 12.0 ⁇ m, 11.5 ⁇ m, 11.0 ⁇ m, 10.5 ⁇ m, 10.0 ⁇ m, 9.5 ⁇ m, 9.0 ⁇ m, 8.5 ⁇ m, 8.0 ⁇ m, 7.5 ⁇ m, 7.0
  • the particle diameter Dv50 of the second silicon oxide is 0.4 ⁇ m to 4.0 ⁇ m.
  • the lower limit value of the particle size Dv50 of the second silicon oxide may be selected from 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m , 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, 2.0 ⁇ m
  • the upper limit of the particle size Dv50 of the second silicon oxide can be selected from 4.0 ⁇ m, 3.9 ⁇ m, 3.8 ⁇ m, 3.7 ⁇ m, 3.6 ⁇ m, 3.5 ⁇ m, 3.4 ⁇ m, 3.3 ⁇ m, 3.2 ⁇ m, 3.1 ⁇ m, 3.0 ⁇ m, 2.9 ⁇ m, 2.8 ⁇ m, 2.7 ⁇ m, 2.6 ⁇ m, 2.5 ⁇ m, 2.4 ⁇ m, 2.3 ⁇ m, 2.2
  • the particle size Dv50 of the negative electrode active material is 3.5 ⁇ m to 10.5 ⁇ m.
  • the lower limit value of the particle size Dv50 of the negative electrode active material may be selected from 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m, 5.0 ⁇ m, 5.5 ⁇ m, 6.0 ⁇ m, 6.5 ⁇ m, 7.0 ⁇ m, and the particles of the negative electrode active material
  • the upper limit value of the diameter Dv50 may be selected from 10.5 ⁇ m, 10.0 ⁇ m, 9.5 ⁇ m, 9.0 ⁇ m, 8.5 ⁇ m, 8.0 ⁇ m, 7.5 ⁇ m, 7.0 ⁇ m, 6.5 ⁇ m. More preferably, the particle diameter Dv50 of the negative electrode active material is 4.0 ⁇ m to 8.5 ⁇ m.
  • the occurrence of the first silicon oxide and the second silicon oxide and the electrolyte can also be greatly reduced The probability of side effects.
  • the ratio of the specific surface area of the first silicon oxide to the specific surface area of the second silicon oxide is 1: (1.5 to 13.0); more preferably, the specific surface area of the first silicon oxide is The ratio of the specific surface area of the second silicon oxide is 1: (1.8 to 10.0).
  • the specific surface area of the first silicon oxide is 0.4m 2 /g ⁇ 3.2m 2 / g.
  • said surface area than the lower limit of the first silicon oxide may optionally from 0.4m 2 /g,0.5m 2 /g,0.6m 2 /g,0.7m 2 /g,0.8m 2 / g, 0.9m 2 /g,1.0m 2 /g,1.1m 2 /g,1.2m 2 /g,1.3m 2 /g,1.4m 2 / g, 1.5m 2 /g,1.6m 2 /g,1.7m 2 /g,1.8m 2 / g
  • the specific surface area of the first upper limit may be optionally selected from silicon oxide 3.2m 2 /g,3.1m 2 /g,3.0m 2 /g,2.9m 2 / g, 2.8m 2 /g,2.7m 2 /g,2.6m 2 /g,2.5m 2 /g,2.4m 2 /g,2.3m 2 /g,2.2m 2 /g
  • the second silicon oxide specific surface area is 4.6m 2 /g ⁇ 12.5m 2 / g.
  • the lower limit of the specific surface area of the second silicon oxide may optionally from 4.6m 2 /g,4.8m 2 /g,5.0m 2 /g,5.2m 2 /g,5.5m 2 / g, 6.0m 2 /g,6.5m 2 /g,7.0m 2 /g,7.5m 2 /g,8.0m 2 /g,8.5m 2 /g,9.0m 2 / g
  • the second silicon oxide surface area than the upper limit may be optionally selected from 12.5m 2 /g,12.0m 2 /g,11.5m 2 /g,11.0m 2 /g,10.5m 2 /g,10.0m 2 /g,9.5m 2 / g, 9.0m 2 /g,8.5m 2 /g,8.0m 2 / g.
  • the specific surface area of the second silicon oxide is 5.0m 2 /g ⁇ 1
  • the specific surface area of the negative electrode active material is 1.8m 2 /g ⁇ 5.9m 2 / g.
  • the lower limit value of the specific surface area of the negative electrode active material may be selected from 1.8m 2 / g, 2.0m 2 / g, 2.2m 2 / g, 2.4m 2 / g, 2.6m 2 / g, 2.8m 2 /g,3.0m 2 /g,3.2m 2 /g,3.5m 2 / g
  • the upper limit of the specific surface area of the negative electrode active material may be optionally selected from 5.9m 2 /g,5.6m 2 / g, 5.4m 2 /g,5.2m 2 /g,5.0m 2 /g,4.8m 2 /g,4.5m 2 /g,4.0m 2 /g,3.5m 2 / g. More preferably, the negative active material specific surface area of 2.4m 2 /g ⁇ 5.2m 2 / g.
  • the amount of negative active material added is also controlled within a certain range.
  • the weight ratio of the first silicon oxide to the second silicon oxide is (60% to 90%): (40% to 10%); more preferably, the first silicon oxide and The weight ratio of the second silicon oxide is (75% to 90%): (25% to 10%).
  • the negative electrode active material of the present application preferably, has a compact density of 0.8 g/cm 3 to 2.0 g/cm 3 under a test condition with a pressure of 5 tons; more preferably, the negative electrode The compacted density of the active material under test conditions with a pressure of 5 tons is 1.1 g/cm 3 to 1.7 g/cm 3 .
  • the anode active material of the present application preferably, the anode active material further includes a coating layer coated on the surface of at least one of the first silicon oxide and the second silicon oxide.
  • the coating layer may preferably include one or more of carbon-based materials, metals, and metal oxides.
  • the carbon-based material may preferably be one selected from natural graphite, artificial graphite, conductive carbon black, superconducting carbon black, acetylene black, Ketjen black, amorphous carbon, coke, mesophase carbon microspheres, carbon fiber Or several;
  • the metal may be preferably selected from one or more of Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn, Mg;
  • the metal oxide may be preferably selected from Al, Ti, Fe , Ni, Cu, Zn, Ag, Sn, Mg one or more oxides.
  • the first silicon oxide and/or the second silicon oxide may be silicon oxides pre-doped with lithium.
  • the molecular formula of the negative electrode active material is SiOx, 0 ⁇ x ⁇ 2.
  • the negative electrode active material may be obtained by a grading and screening method, and the grading and screening may be airflow grading or sieve screening.
  • the particle sizes of the first silicon oxide, the second silicon oxide, and the negative electrode active material can be measured using a laser diffraction method, based on the particle size distribution laser diffraction method GB/T19077- In 2016, the number particle size distribution and volume particle size distribution were measured; the specific surface area of the first silicon oxide, the second silicon oxide, and the negative electrode active material can be measured using the BET method.
  • the negative electrode sheet according to the second aspect of the present application includes a negative electrode current collector and a negative electrode membrane provided on at least one surface of the negative electrode current collector and including the negative electrode active material according to the first aspect of the present application.
  • the negative electrode diaphragm may be provided on one surface of the negative electrode current collector or on both surfaces of the negative electrode current collector.
  • the negative electrode membrane may further include other negative electrode active materials, such as carbon materials.
  • the carbon material is selected from one or more of graphite, soft carbon, hard carbon, mesophase carbon microspheres, carbon fibers, and carbon nanotubes.
  • the negative electrode membrane may further include a conductive agent and a binder, wherein the types and contents of the conductive agent and the binder are not specifically limited, and can be selected according to actual needs.
  • the type of the negative electrode current collector is also not specifically limited, and can be selected according to actual needs.
  • the battery of the present application includes a positive pole piece, a negative pole piece, a separator, an electrolyte, and the like.
  • the negative electrode sheet may include a negative electrode current collector and a negative electrode membrane provided on at least one surface of the negative electrode current collector and including the negative electrode active material according to the first aspect of the present application, the negative electrode membrane may be provided on the negative electrode One surface of the current collector may be provided on both surfaces of the negative electrode current collector.
  • the negative electrode diaphragm may further include other negative electrode active materials, such as carbon materials.
  • the carbon material is selected from one or more of graphite, soft carbon, hard carbon, mesophase carbon microspheres, carbon fibers, and carbon nanotubes.
  • the negative electrode diaphragm may further include a conductive agent and a binder, wherein the types and contents of the conductive agent and the binder are not specifically limited, and can be selected according to actual needs.
  • the type of the negative electrode current collector is also not specifically limited, and can be selected according to actual needs.
  • the positive electrode sheet may include a positive electrode current collector and a positive electrode membrane provided on at least one surface of the positive electrode current collector and including a positive electrode active material, and the positive electrode membrane may be provided in the positive electrode current collector One surface may be provided on both surfaces of the positive electrode current collector.
  • the positive electrode diaphragm may further include a conductive agent and a binder, wherein the types and contents of the conductive agent and the binder are not specifically limited, and can be selected according to actual needs.
  • the type of the positive electrode current collector is also not specifically limited, and can be selected according to actual needs.
  • the battery in the third aspect of the present application may be a lithium ion battery, a sodium ion battery, and any other battery using the negative electrode active material described in the first aspect of the present application.
  • the positive electrode active material may be selected from lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide , Lithium-containing phosphate with olivine structure, etc., but the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for lithium ion batteries can also be used. Only one kind of these positive electrode active materials may be used alone, or two or more kinds may be used in combination.
  • the positive electrode active material may be selected from LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM333), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), LiNi 0.85 Co 0.15 Al 0.05 O 2 , LiFePO 4 (LFP), LiMnPO 4 Or several.
  • the positive electrode active material may be selected from the transition metal oxide Na x MO 2 (M is a transition metal, preferably one selected from Mn, Fe, Ni, Co, V, Cu, Cr Or several, 0 ⁇ x ⁇ 1), polyanionic materials (phosphate, fluorophosphate, pyrophosphate, sulfate type), Prussian blue materials, etc., but this application is not limited to these materials, this application can also Other conventionally known materials that can be used as positive electrode active materials for sodium ion batteries are used. Only one kind of these positive electrode active materials may be used alone, or two or more kinds may be used in combination.
  • M is a transition metal, preferably one selected from Mn, Fe, Ni, Co, V, Cu, Cr Or several, 0 ⁇ x ⁇ 1
  • polyanionic materials phosphate, fluorophosphate, pyrophosphate, sulfate type
  • Prussian blue materials etc.
  • the positive electrode active material may be selected from NaFeO 2 , NaCoO 2 , NaCrO 2 , NaMnO 2 , NaNiO 2 , NaNi 1/2 Ti 1/2 O 2 , NaNi 1/2 Mn 1/2 O 2 , Na 2 / 3 Fe 1/3 Mn 2/3 O 2 , NaNi 1/3 Co 1/3 Mn 1/3 O 2, NaFePO 4, NaMnPO 4, NaCoPO 4, Prussian blue materials, the general formula A a M b (PO 4 ) Materials of c O x Y 3-x (where A is selected from one or more of H + , Li + , Na + , K + , NH 4+ , M is a transition metal cation, preferably selected from V, One or more of Ti, Mn, Fe, Co, Ni, Cu, Zn, Y is a halogen anion, preferably one or more selected from F, Cl, Br, 0 ⁇ a ⁇ 4, 0 ⁇ One or more of b ⁇ 2, 1 ⁇ c ⁇ 3, 0
  • the separator is provided between the positive pole piece and the negative pole piece to play a role of isolation.
  • the type of the separator is not specifically limited, and may be any separator material used in existing batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, and their multilayer composite membranes, but not limited to These ones.
  • the type of the electrolyte is not specifically limited, and may be a liquid electrolyte (also called an electrolyte) or a solid electrolyte.
  • the electrolyte uses a liquid electrolyte.
  • the liquid electrolyte may include an electrolyte salt and an organic solvent, and the types of the electrolyte salt and the organic solvent are not subject to specific restrictions, and can be selected according to actual needs.
  • the electrolyte may further include additives, and the types of the additives are not particularly limited, and may be negative electrode film-forming additives, positive electrode film-forming additives, or additives that can improve certain performances of the battery, such as improving battery performance. Additives for charging performance, additives for improving high temperature performance of batteries, additives for improving low temperature performance of batteries, etc.
  • the battery may include an outer package for encapsulating the positive electrode tab, the negative electrode tab, and the electrolyte.
  • the positive pole piece, the negative pole piece and the separator can be laminated or wound to form a laminated structure electrode assembly or a wound structure electrode assembly, and the electrode assembly is encapsulated in an outer package;
  • the electrolyte can be an electrolyte, which is infiltrated by the electrolyte In the electrode assembly.
  • the number of electrode assemblies in the battery can be one or several, which can be adjusted according to requirements.
  • the outer packaging of the battery may be a soft bag, such as a pouch type soft bag.
  • the material of the soft bag may be plastic, such as one or more of polypropylene PP, polybutylene terephthalate PBT, polybutylene succinate PBS, etc.
  • the outer packaging of the battery can also be a hard shell, such as an aluminum shell.
  • the shape of the battery in this application which may be cylindrical, square, or any other shape.
  • the battery 5 has a square structure as an example.
  • the battery may be assembled into a battery module, and the number of batteries contained in the battery module may be multiple, and the specific number may be adjusted according to the application and capacity of the battery module.
  • FIG. 2 is a battery module 4 as an example.
  • a plurality of batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other way. Further, the plurality of batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of batteries 5 are accommodated in the accommodation space.
  • the above battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery case includes an upper case 2 and a lower case 3.
  • the upper case 2 can be covered on the lower case 3 and forms an enclosed space for accommodating the battery module 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • an apparatus in a fourth aspect of the present application, includes the battery of the third aspect of the present application, and the battery provides power for the apparatus.
  • the device may be, but not limited to, mobile equipment (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf balls) Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a battery, battery module or battery pack according to its usage requirements.
  • Fig. 5 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, or the like.
  • the device is usually required to be thin and light, and a battery can be used as a power source.
  • the batteries of Examples 1-14 and Comparative Examples 1-4 were prepared according to the following methods.
  • the negative electrode active material (see Table 1 for details), the conductive agent Super P, the thickener sodium carboxymethyl cellulose (CMC), and the binder styrene-butadiene rubber (SBR) in a mass ratio of 80:10:5:5.
  • Add solvent deionized water and stir under the action of a vacuum mixer until the system is uniform to obtain a negative electrode slurry; apply the negative electrode slurry uniformly on the negative electrode current collector copper foil, and then apply the negative electrode slurry coated negative electrode slurry
  • the fluid was dried at room temperature and transferred to an oven to continue drying, and then cold-pressed and slit to obtain a negative pole piece.
  • Ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC) are mixed in a volume ratio of 1:1:1 to obtain an organic solvent, and then the fully dried lithium salt LiPF 6 is dissolved in the mixture After the organic solvent is prepared, a concentration of 1mol/L electrolyte is prepared.
  • Polyethylene film is used as isolation film.
  • the thickness rebound rate of the negative pole piece [ (D2-D0)/(D1-D0)-1] ⁇ 100%.
  • the particle size Dn10 of the first silicon oxide is small, resulting in a ratio of the particle size Dn10 of the first silicon oxide to the particle size Dn10 of the second silicon oxide that is too low (less than 8), and the first silicon oxide is oxidized
  • the particle size distribution of the substance is narrow and the particle size distribution of the second silicon oxide is wide.
  • the negative pole piece prepared in this way contains a large amount of fine particles, which may easily lead to excessive consumption of the electrolyte and deteriorate the cycle performance of the battery.
  • the particle diameter Dn10 of the second silicon oxide is relatively large, which results in the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide being too low (less than 8), and the second silicon oxide is oxidized.
  • the particle size distribution of the object is narrow, so that the matching of the two silicon oxides will be poor, and the quantity advantage of the second silicon oxide is almost lost.
  • the ratio of the particle diameter Dn10 of the first silicon oxide to the particle diameter Dn10 of the second silicon oxide in Comparative Examples 3 and 4 is too high (greater than 25), and the prepared negative pole piece will contain a large amount of fine The particles easily lead to increased consumption of the electrolyte and deteriorate the cycle performance of the battery. At the same time, the presence of a large number of fine particles will also increase the thickness rebound rate of the negative pole piece.
  • the particle size distribution of the second silicon oxide in Comparative Example 3 and Comparative Example 4 is narrow, so that the matching of the two silicon oxides will be poor, and the second silicon oxide with a smaller Dn10 is filled as a filler in The effect of the gap in the first silicon oxide with a larger Dn10 is poorer, and also increases the thickness rebound rate of the negative pole piece.

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Abstract

一种负极活性材料、电池（5）及装置。所述负极活性材料包括第一硅氧化物以及第二硅氧化物，其中，所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值为8～25，所述第一硅氧化物的粒径Dn10为1.0μm～5.0μm，所述第二硅氧化物的粒径Dn10为0.05μm～0.50μm。通过选择两种具有特定Dn10范围的硅氧化物进行搭配来控制负极极片的厚度反弹，保证负极活性材料之间的良好的电接触，进而有助于提升电池（5）的循环稳定性和循环寿命。

Description

负极活性材料、电池及装置 技术领域
本申请涉及电池领域，尤其涉及一种负极活性材料、电池及装置。
背景技术
近年来，由于电动汽车产业对能量密度的更高要求，人们围绕高容量负极活性材料开展了大量研究。其中，硅由于具有高于石墨十倍以上的理论克容量而受到重视，但是硅存在严重的体积效应，充电过程中会产生巨大的体积膨胀。由此采用硅作为负极活性材料制成的负极极片在电池使用过程中的厚度反弹较大且负极极片的孔隙率也较高，这样负极极片结构从初始的致密状态逐渐变成疏松多孔的状态，负极极片的导电网络受到损坏，负极活性材料之间的电接触变差，严重影响了电池的循环稳定性和循环寿命。
发明内容
鉴于背景技术中存在的问题，本申请的目的在于提供一种负极活性材料、电池及装置，本申请能控制负极极片的厚度反弹，保证负极活性材料之间的良好的电接触，并提升电池的循环稳定性和循环寿命。
为了达到上述目的，在本申请的第一方面，本申请提供了一种负极活性材料，其包括第一硅氧化物以及第二硅氧化物，其中，所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值为8～25，所述第一硅氧化物的粒径Dn10为1.0μm～5.0μm，所述第二硅氧化物的粒径Dn10为0.05μm～0.50μm。
在本申请的第二方面，本申请提供了一种电池，其包括根据本申请第一方面所述的负极活性材料。
在本申请的第三方面，本申请提供了一种装置，其包括本申请第二方面所述的电池。
本申请至少包括如下所述的有益效果：
本申请通过选择两种具有特定Dn10范围的硅氧化物进行搭配来控制负极极片的厚度反弹，保证负极活性材料之间的良好的电接触，进而有助于提升电池的循环稳定性和循环寿命。本申请的装置包括所述的电池，因而至少具有与所述电池相同的优势。
附图说明
图1是电池的一实施方式的示意图。
图2是电池模块的一实施方式的示意图。
图3是电池包的一实施方式的示意图。
图4是图3的分解图。
图5是电池用作电源的装置的一实施方式的示意图。
其中，附图标记说明如下：
1电池包
2上箱体
3下箱体
4电池模块
5电池
具体实施方式
下面详细说明根据本申请的负极活性材料、电池及装置。
首先说明根据本申请第一方面的负极活性材料。
根据本申请第一方面的负极活性材料包括第一硅氧化物以及第二硅氧化物，其中，所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值为8～25，所述第一硅氧化物的粒径Dn10为1.0μm～5.0μm，所述第二硅氧化物的粒径Dn10为0.05μm～0.50μm。需要说明的是，Dn10表示累计数量百分数达到10％时所对应的粒径。
所述第一硅氧化物的粒径Dn10不宜过高，否则负极活性材料中细小颗粒含量过少，对抑制负极极片的厚度反弹不利。其中，所述第一硅氧化物的粒径Dn10的下限值可任选自1.0μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm、2.0μm，所述第一硅氧化物的粒径Dn10的 上限值可任选自5.0μm、4.8μm、4.5μm、4.2μm、4.0μm、3.8μm、3.6μm、3.4μm、3.2μm、3.0μm、2.8μm、2.6μm、2.4μm、2.0μm。优选地，所述第一硅氧化物的粒径Dn10为1.7μm～4.5μm。
所述第二硅氧化物的粒径Dn10不宜过小，否则制备的负极极片中将含有大量的细小颗粒，容易导致对电解液的消耗增加，恶化电池的循环性能和使用寿命。其中，所述第二硅氧化物的粒径Dn10的下限值可任选自0.05μm、0.06μm、0.07μm、0.08μm、0.09μm、0.10μm、0.11μm、0.12μm、0.13μm、0.14μm、0.15μm，所述第二硅氧化物的粒径Dn10的上限值可任选自0.50μm、0.48μm、0.45μm、0.40μm、0.38μm、0.35μm、0.32μm、0.30μm、0.28μm、0.26μm、0.24μm、0.22μm、0.20μm、0.18μm。优选地，所述第二硅氧化物的粒径Dn10为0.10μm～0.35μm。
所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值的下限值可任选自8、9、10、11、12、13、14、15、16，所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值的上限值可任选自25、24、23、22、21、20、19、18、17、16、15。优选地，所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值为10～20。
在本申请的负极活性材料中，将两种具有特定Dn10范围的硅氧化物混合搭配后，可以有效地降低负极极片的厚度反弹，并保持负极活性材料之间良好的电接触，从而有助于提升电池的循环稳定性和循环寿命。可能的原因在于：从负极活性材料粉体层面来看，不同Dn10范围的第一硅氧化物和第二硅氧化物混合搭配的方式能大大提高负极活性材料粉体的压实密度，而压实密度越大表明负极活性材料粉体之间的匹配程度越高，越有利于负极极片压实密度的提升，且负极活性材料之间的电接触也越好；从负极极片层面来看，在制备负极极片的过程中，Dn10较小的第二硅氧化物由于具有更小的粒径且数量更多，填充在Dn10较大的第一硅氧化物之间的间隙中后，不仅能提升负极极片的压实密度，而且能在电池使用过程中降低由于Dn10较大的第一硅氧化物体积膨胀而导致负极极片中较大空隙出现的概率，即能降低负极极片的厚度反弹和孔隙率，从而能提升电池的循环稳定性和循环寿命。
所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值过低，Dn10较小的第二硅氧化物的数量优势几乎丧失，难以将Dn10较大 的第一硅氧化物之间的间隙填满，在电池使用过程中，负极极片的厚度反弹较大。所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值过高，制备的负极极片中将含有大量的细小颗粒，容易导致对电解液的消耗增加，恶化电池的循环性能和使用寿命。
Dn10表示累计数量百分数达到10％时所对应的粒径，即粒径小于Dn10对应粒径的颗粒数量占所有颗粒总数量的10％，其能更为准确和直观地反映细小颗粒的含量。而体积粒径则是表示粒径小于某一数值的颗粒总体积占所有颗粒总体积的百分比。对于粒径分布范围较广的粉料(例如负极活性材料)而言，细小颗粒的粉料在负极活性材料粉料中的体积百分比微不足道，但是细小颗粒的粉料对负极活性材料粉料(尤其是含硅负极活性材料粉料)的体积膨胀有很大影响，因此用常规的体积粒径来表征负极活性材料粉料中细小颗粒的含量比较粗略，而用数量粒径来表征负极活性材料粉料中细小颗粒的含量则更加精确和直观，进而对合理控制负极极片的厚度反弹有利。
在本申请的负极活性材料中，优选地，所述负极活性材料的粒径Dn10为0.10μm～0.50μm。其中，所述负极活性材料的粒径Dn10的下限值可任选自0.10μm、0.11μm、0.12μm、0.13μm、0.14μm、0.15μm、0.16μm、0.17μm、0.18μm、0.19μm、0.20μm，所述负极活性材料的粒径Dn10的上限值可任选自0.50μm、0.48μm、0.45μm、0.42μm、0.40μm、0.38μm、0.35μm、0.32μm、0.30μm、0.28μm、0.26μm、0.24μm、0.22μm、0.20μm。更优选地，所述负极活性材料的粒径Dn10为0.15μm～0.36μm。
在本申请的负极活性材料中，通过选择两种具有特定Dn10范围的硅氧化物进行搭配，可以很好地控制负极极片的厚度反弹和孔隙率增加，使负极活性材料之间保持良好的电接触，在此基础上，如果进一步合理控制两种硅氧化物的粒径分布宽度，还有利于提升负极活性材料颗粒间的匹配程度，维持良好的电极结构，从而能进一步提升电池的循环稳定性和循环寿命。其中，粒径分布宽度用(Dn90-Dn10)/Dn50表示。Dn10、Dn50、Dn90分别表示累计数量百分数达到10％、50％、90％时所对应的粒径。
优选地，所述第一硅氧化物具有0.8～1.2的粒径分布宽度。所述第一硅氧化物的粒径分布宽度的下限值可任选自0.80、0.82、0.84、0.86、0.88、0.90、0.92、0.94、0.96、0.98、1.00，所述第一硅氧化物的粒径分布宽度的上限值 可任选自1.20、1.18、1.16、1.14、1.12、1.10、1.08、1.06、1.04、1.02、1.00。更优选地，所述第一硅氧化物具有0.9～1.1的粒径分布宽度。
所述第二硅氧化物的粒径分布越宽，第二硅氧化物的数量优势越好，但同时制备的负极极片中将含有大量的细小颗粒，对电解液的消耗越大；所述第二硅氧化物的粒径分布越窄，第二硅氧化物的数量优势越差，作为填充物填充在第一硅氧化物间隙中的效果越差。优选地，所述第二硅氧化物具有1.0～1.6的粒径分布宽度。所述第二硅氧化物的粒径分布宽度的下限值可任选自1.00、1.02、1.04、1.06、1.08、1.10、1.12、1.14、1.16、1.18、1.20、1.22、1.24、1.26、1.28、1.30，所述第二硅氧化物的粒径分布宽度的上限值可任选自1.60、1.58、1.56、1.54、1.52、1.50、1.48、1.46、1.44、1.42、1.40、1.38、1.36、1.34、1.32、1.30。更优选地，所述第二硅氧化物具有1.1～1.5的粒径分布宽度。
优选地，所述负极活性材料具有1.0～1.5的粒径分布宽度。所述负极活性材料的粒径分布宽度的下限值可任选自1.00、1.02、1.04、1.06、1.08、1.10、1.12、1.14、1.16、1.18、1.20、1.22、1.25，所述负极活性材料的粒径分布宽度的上限值可任选自1.50、1.48、1.46、1.44、1.42、1.40、1.38、1.36、1.34、1.32、1.30、1.28、1.25。更优选地，所述负极活性材料具有1.1～1.4的粒径分布宽度。
在本申请的负极活性材料中，通过选择两种具有特定Dn10范围的硅氧化物进行搭配，可以很好地控制负极极片的厚度反弹和孔隙率增加，使负极活性材料之间保持良好的电接触，在此基础上，如果进一步合理控制两种硅氧化物的平均体积粒径，还有利于促进活性离子在负极活性材料中的脱出和嵌入，从而能进一步提升电池的循环稳定性和循环寿命。其中，平均体积粒径用Dv50表示，Dv50表示累计体积百分数达到50％时所对应的粒径。
优选地，所述第一硅氧化物的粒径Dv50与所述第二硅氧化物的粒径Dv50的比值为1.0～8.0。其中，所述第一硅氧化物的粒径Dv50与所述第二硅氧化物的粒径Dv50的比值的下限值可任选自1.0、1.1、1.2、1.3、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5，所述第一硅氧化物的粒径Dv50与所述第二硅氧化物的粒径Dv50的比值的上限值可任选自8.0、7.6、7.2、6.8、6.4、6.0、5.6、5.2、4.8、4.4、4.0、3.6、3.2、2.8、2.4、2.0。更优选地， 所述第一硅氧化物的粒径Dv50与所述第二硅氧化物的粒径Dv50的比值为1.5～7.2。
优选地，所述第一硅氧化物的粒径Dv50为3.0μm～15.0μm。其中，所述第一硅氧化物的粒径Dv50的下限值可任选自3.0μm、3.2μm、3.4μm、3.6μm、3.8μm、4.0μm、4.2μm、4.4μm、4.6μm、4.8μm、5.0μm、5.2μm、5.4μm、5.6μm、5.8μm、6.0μm，所述第一硅氧化物的粒径Dv50的上限值可任选自15.0μm、14.5μm、14.0μm、13.5μm、13.0μm、12.5μm、12.0μm、11.5μm、11.0μm、10.5μm、10.0μm、9.5μm、9.0μm、8.5μm、8.0μm、7.5μm、7.0μm、6.5μm、6.0μm。更优选地，所述第一硅氧化物的粒径Dv50为4.4μm～11.0μm。
优选地，所述第二硅氧化物的粒径Dv50为0.4μm～4.0μm。其中，所述第二硅氧化物的粒径Dv50的下限值可任选自0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1.0μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm、2.0μm，所述第二硅氧化物的粒径Dv50的上限值可任选自4.0μm、3.9μm、3.8μm、3.7μm、3.6μm、3.5μm、3.4μm、3.3μm、3.2μm、3.1μm、3.0μm、2.9μm、2.8μm、2.7μm、2.6μm、2.5μm、2.4μm、2.3μm、2.2μm、2.1μm、2.0μm。更优选地，所述第二硅氧化物的粒径Dv50为0.9μm～3.5μm。
优选地，所述负极活性材料的粒径Dv50为3.5μm～10.5μm。其中，所述负极活性材料的粒径Dv50的下限值可任选自3.5μm、4.0μm、4.5μm、5.0μm、5.5μm、6.0μm、6.5μm、7.0μm，所述负极活性材料的粒径Dv50的上限值可任选自10.5μm、10.0μm、9.5μm、9.0μm、8.5μm、8.0μm、7.5μm、7.0μm、6.5μm。更优选地，所述负极活性材料的粒径Dv50为4.0μm～8.5μm。
在本申请的负极活性材料中，通过进一步合理调节第一硅氧化物的比表面积和第二硅氧化物的比表面积，还可以大大减少第一硅氧化物和第二硅氧化物与电解液发生副反应的概率。
优选地，所述第一硅氧化物的比表面积与所述第二硅氧化物的比表面积的比值为1：(1.5～13.0)；更优选地，所述第一硅氧化物的比表面积与所述第二硅氧化物的比表面积的比值为1：(1.8～10.0)。
优选地，所述第一硅氧化物的比表面积为0.4m 2/g～3.2m 2/g。其中，所述第一硅氧化物的比表面积的下限值可任选自0.4m 2/g、0.5m 2/g、0.6m 2/g、0.7m 2/g、0.8m 2/g、0.9m 2/g、1.0m 2/g、1.1m 2/g、1.2m 2/g、1.3m 2/g、1.4m 2/g、 1.5m 2/g、1.6m 2/g、1.7m 2/g、1.8m 2/g，所述第一硅氧化物的比表面积的上限值可任选自3.2m 2/g、3.1m 2/g、3.0m 2/g、2.9m 2/g、2.8m 2/g、2.7m 2/g、2.6m 2/g、2.5m 2/g、2.4m 2/g、2.3m 2/g、2.2m 2/g、2.1m 2/g、2.0m 2/g、1.9m 2/g、1.8m 2/g。更优选地，所述第一硅氧化物的比表面积为0.8m 2/g～2.5m 2/g。
优选地，所述第二硅氧化物的比表面积为4.6m 2/g～12.5m 2/g。其中，所述第二硅氧化物的比表面积的下限值可任选自4.6m 2/g、4.8m 2/g、5.0m 2/g、5.2m 2/g、5.5m 2/g、6.0m 2/g、6.5m 2/g、7.0m 2/g、7.5m 2/g、8.0m 2/g、8.5m 2/g、9.0m 2/g，所述第二硅氧化物的比表面积的上限值可任选自12.5m 2/g、12.0m 2/g、11.5m 2/g、11.0m 2/g、10.5m 2/g、10.0m 2/g、9.5m 2/g、9.0m 2/g、8.5m 2/g、8.0m 2/g。更优选地，所述第二硅氧化物的比表面积为5.0m 2/g～10.0m 2/g。
优选地，所述负极活性材料的比表面积为1.8m 2/g～5.9m 2/g。其中，所述负极活性材料的比表面积的下限值可任选自1.8m 2/g、2.0m 2/g、2.2m 2/g、2.4m 2/g、2.6m 2/g、2.8m 2/g、3.0m 2/g、3.2m 2/g、3.5m 2/g，所述负极活性材料的比表面积的上限值可任选自5.9m 2/g、5.6m 2/g、5.4m 2/g、5.2m 2/g、5.0m 2/g、4.8m 2/g、4.5m 2/g、4.0m 2/g、3.5m 2/g。更优选地，所述负极活性材料的比表面积为2.4m 2/g～5.2m 2/g。
在本申请的负极活性材料中，当负极活性材料的粒径较小时其比表面积通常也较大，且在电池使用过程中对电解液和活性离子的消耗也很大，因此优选将小颗粒的负极活性材料的加入量也控制在一定范围内。
优选地，所述第一硅氧化物与所述第二硅氧化物的重量比为(60％～90％)：(40％～10％)；更优选地，所述第一硅氧化物与所述第二硅氧化物的重量比为(75％～90％)：(25％～10％)。
在本申请的负极活性材料中，优选地，所述负极活性材料在压力为5吨的测试条件下的压实密度为0.8g/cm 3～2.0g/cm 3；更优选地，所述负极活性材料在压力为5吨的测试条件下的压实密度为1.1g/cm 3～1.7g/cm 3。
在本申请的负极活性材料中，优选地，所述负极活性材料进一步包括包覆在所述第一硅氧化物和所述第二硅氧化物中的至少一个的表面上的涂层。所述涂层可优选包括碳类材料、金属、金属氧化物中的一种或几种。
其中，所述碳类材料可优选选自天然石墨、人造石墨、导电碳黑、超导碳黑、乙炔黑、科琴黑、无定形碳、焦炭、中间相碳微球、碳纤维中的一种 或几种；所述金属可优选选自Al、Ti、Fe、Ni、Cu、Zn、Ag、Sn、Mg中的一种或几种；所述金属氧化物可优选选自Al、Ti、Fe、Ni、Cu、Zn、Ag、Sn、Mg中的一种或几种的氧化物。
在本申请的负极活性材料中，优选地，所述第一硅氧化物和/或所述第二硅氧化物可为预掺杂锂的硅氧化物。
在本申请的负极活性材料中，所述负极活性材料的分子式为SiOx，0＜x≤2。
在本申请的负极活性材料中，所述负极活性材料可通过分级筛选方法得到，所述分级筛选可为气流分级或筛网过筛分级。
在本申请的负极活性材料中，所述第一硅氧化物、所述第二硅氧化物以及所述负极活性材料的粒径可以使用激光衍射法测量，依据粒度分布激光衍射法GB/T19077-2016，测量出数量粒径分布和体积粒径分布；所述第一硅氧化物、所述第二硅氧化物以及所述负极活性材料的比表面积可以使用BET法测量。
其次说明根据本申请第二方面的负极极片。
根据本申请第二方面的负极极片包括负极集流体以及设置在负极集流体至少一个表面上且包括根据本申请第一方面所述的负极活性材料的负极膜片。
在本申请的负极极片中，所述负极膜片可设置在负极集流体的其中一个表面上也可以设置在负极集流体的两个表面上。
在本申请的负极极片中，除了包括根据本申请第一方面所述的负极活性材料外，所述负极膜片还可包括其它负极活性材料，例如碳材料。优选地，所述碳材料选自石墨、软碳、硬碳、中间相碳微球、碳纤维、碳纳米管中的一种或几种。
在本申请的负极极片中，所述负极膜片还可包括导电剂以及粘结剂，其中导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。
在本申请的负极极片中，所述负极集流体的种类也不受具体的限制，可根据实际需求进行选择。
再次说明根据本申请第三方面的电池。
本申请的电池包括正极极片、负极极片、隔离膜以及电解质等。其中，所述负极极片可包括负极集流体以及设置在负极集流体至少一个表面上且包括根据本申请第一方面所述的负极活性材料的负极膜片，所述负极膜片可设置在负极集流体的其中一个表面上也可以设置在负极集流体的两个表面上。除了包括根据本申请第一方面所述的负极活性材料外，所述负极膜片还可包括其它负极活性材料，例如碳材料。优选地，所述碳材料选自石墨、软碳、硬碳、中间相碳微球、碳纤维、碳纳米管中的一种或几种。所述负极膜片还可包括导电剂以及粘结剂，其中，导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。所述负极集流体的种类也不受具体的限制，可根据实际需求进行选择。
在本申请的电池中，所述正极极片可包括正极集流体以及设置在正极集流体至少一个表面上且包括正极活性材料的正极膜片，所述正极膜片可设置在正极集流体的其中一个表面上也可以设置在正极集流体的两个表面上。所述正极膜片还可包括导电剂以及粘结剂，其中，导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。所述正极集流体的种类也不受具体的限制，可根据实际需求进行选择。
需要说明的是，本申请第三方面的电池可为锂离子电池、钠离子电池以及任何其它使用本申请第一方面所述负极活性材料的电池。
当电池为锂离子电池时：所述正极活性材料可选自锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物、橄榄石结构的含锂磷酸盐等，但本申请并不限定于这些材料，还可以使用其他可被用作锂离子电池正极活性材料的传统公知的材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。优选地，所述正极活性材料可选自LiCoO 2、LiNiO 2、LiMnO 2、LiMn 2O 4、LiNi 1/3Co 1/3Mn 1/3O 2(NCM333)、LiNi 0.5Co 0.2Mn 0.3O 2(NCM523)、LiNi 0.6Co 0.2Mn 0.2O 2(NCM622)、LiNi 0.8Co 0.1Mn 0.1O 2(NCM811)、LiNi 0.85Co 0.15Al 0.05O 2、LiFePO 4(LFP)、LiMnPO 4中的一种或几种。
当电池为钠离子电池时：所述正极活性材料可选自过渡金属氧化物 Na xMO 2(M为过渡金属，优选选自Mn、Fe、Ni、Co、V、Cu、Cr中的一种或几种，0<x≤1)、聚阴离子材料(磷酸盐、氟磷酸盐、焦磷酸盐、硫酸盐类型)、普鲁士蓝材料等，但本申请并不限定于这些材料，本申请还可以使用其他可被用作钠离子电池正极活性材料的传统公知的材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。优选地，所述正极活性材料可选自NaFeO 2、NaCoO 2、NaCrO 2、NaMnO 2、NaNiO 2、NaNi 1/2Ti 1/2O 2、NaNi 1/2Mn 1/2O 2、Na 2/3Fe 1/3Mn 2/3O 2、NaNi 1/3Co 1/3Mn 1/3O 2、NaFePO 4、NaMnPO 4、NaCoPO 4、普鲁士蓝材料、通式为A aM b(PO 4) cO xY 3-x的材料(其中A选自H +、Li +、Na +、K +、NH 4+中的一种或几种，M为过渡金属阳离子，优选选自V、Ti、Mn、Fe、Co、Ni、Cu、Zn中的一种或几种，Y为卤素阴离子，优选选自F、Cl、Br中的一种或几种，0<a≤4，0<b≤2，1≤c≤3，0≤x≤2)中的一种或几种。
在本申请的电池中，所述隔离膜设置在正极极片和负极极片之间，起到隔离的作用。其中，所述隔离膜的种类并不受到具体的限制，可以是现有电池中使用的任何隔离膜材料，例如聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜，但不仅限于这些。
在本申请的电池中，所述电解质的种类并不受到具体的限制，可以为液体电解质(又称电解液)，也可以为固体电解质。优选地，所述电解质使用液体电解质。其中，所述液体电解质可包括电解质盐以及有机溶剂，电解质盐以及有机溶剂的种类均不受到具体的限制，可根据实际需求进行选择。所述电解质还可包括添加剂，所述添加剂的种类也没有特别的限制，可以为负极成膜添加剂，也可为正极成膜添加剂，也可以为能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温性能的添加剂、改善电池低温性能的添加剂等。
在一些实施例中，电池可以包括外包装，用于封装正极极片、负极极片和电解质。作为一个示例，正极极片、负极极片和隔离膜可经叠片或卷绕形成叠片结构电极组件或卷绕结构电极组件，电极组件封装在外包装内；电解质可采用电解液，电解液浸润于电极组件中。电池中电极组件的数量可以为一个或几个，可以根据需求来调节。
在一些实施例中，电池的外包装可以是软包，例如袋式软包。软包 的材质可以是塑料，如可包括聚丙烯PP、聚对苯二甲酸丁二醇酯PBT、聚丁二酸丁二醇酯PBS等中的一种或几种。电池的外包装也可以是硬壳，例如铝壳等。
本申请对电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。如图1是作为一个示例的方形结构的电池5。
在一些实施例中，电池可以组装成电池模块，电池模块所含电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
图2是作为一个示例的电池模块4。参照图2，在电池模块4中，多个电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的壳体，多个电池5容纳于该容纳空间。
在一些实施例中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
图3和图4是作为一个示例的电池包1。参照图3和图4，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
接下来说明本申请第四方面的装置。
在本申请第四方面提供一种装置，所述装置包括本申请第三方面的电池，所述电池为所述装置提供电源。所述装置可以但不限于是移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等。
所述装置可以根据其使用需求来选择电池、电池模块或电池包。
图5是作为一个示例的装置。该装置为纯电动车、混合动力电动车、或 插电式混合动力电动车等。为了满足该装置对电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用电池作为电源。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。在本申请的下述具体实施例中，仅示出电池为锂离子电池的实施例，但本申请不限于此。
实施例1-14和对比例1-4的电池均按照下述方法制备。
(1)正极极片的制备
将正极活性材料NCM811、导电剂Super P、粘结剂聚偏氟乙烯(PVDF)按质量比96.8:2.2:1进行混合，加入溶剂N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系呈均一状，获得正极浆料；将正极浆料均匀涂覆在正极集流体铝箔上，之后将涂覆有正极浆料的正极集流体在室温晾干后转移至烘箱继续干燥，然后经过冷压、分切得到正极极片。
(2)负极极片的制备
将负极活性材料(详见表1)、导电剂Super P、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶(SBR)按质量比80:10:5:5进行混合，加入溶剂去离子水，在真空搅拌机作用下搅拌至体系呈均一状，获得负极浆料；将负极浆料均匀涂覆在负极集流体铜箔上，之后将涂覆有负极浆料的负极集流体在室温晾干后转移至烘箱继续干燥，然后经过冷压、分切得到负极极片。
(3)电解液的制备
将碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)按照按体积比1:1:1进行混合得到有机溶剂，接着将充分干燥的锂盐LiPF 6溶解于混合后的有机溶剂中，配制成浓度为1mol/L的电解液。
(4)隔离膜的制备
选用聚乙烯膜作为隔离膜。
(5)电池的制备
将上述正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负 极极片之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装壳中，干燥后注入电解液，经过真空封装、静置、化成、整形等工序，获得电池。
表1实施例1-14和对比例1-4的负极活性材料参数
Figure PCTCN2019125307-appb-000001
接下来说明负极极片以及电池的性能测试。
(1)负极极片的厚度反弹率：
使用万分尺测量负极极片在冷压时的厚度以及在循环5圈后满放状态的厚度，分别记为D1和D2，负极集流体的厚度为D0，则负极极片的厚度反弹率＝[(D2-D0)/(D1-D0)-1]×100％。
(2)电池循环性能：
将制备的电池以1C倍率进行满充和满放，记录容量衰减情况。
表2：实施例1-14和对比例1-4的性能测试结果
Figure PCTCN2019125307-appb-000002
从表2的测试结果可以看出：实施例1-14制备的电池兼具低的负极极片厚度反弹率以及长的循环寿命。
对比例1至对比例4使用的两种硅氧化物尽管具有良好的体积粒径Dv50，但是两种硅氧化物的数量粒径Dn10搭配不理想，会导致负极极片的厚度反弹率变大和循环性能变差。
对比例1中第一硅氧化物的粒径Dn10较小，导致第一硅氧化物的粒径Dn10与第二硅氧化物的粒径Dn10的比值过低(小于8)，且第一硅氧化物的粒径分布较窄而第二硅氧化物的粒径分布较宽，这样制备的负极极片中含有大量的细小颗粒，容易导致对电解液的消耗过大，从而恶化电池的循环性 能。对比例2中第二硅氧化物的粒径Dn10较大，导致第一硅氧化物的粒径Dn10与第二硅氧化物的粒径Dn10的比值过低(小于8)，且第二硅氧化物的粒径分布较窄，这样两种硅氧化物的匹配性会变差，第二硅氧化物的数量优势几乎丧失，作为填充物填充在Dn10较大的第一硅氧化物间隙中的效果较差，在电池使用过程中，负极极片的厚度反弹率较大。
同样地，对比例3和对比例4中第一硅氧化物的粒径Dn10与第二硅氧化物的粒径Dn10的比值过高(大于25)，制备的负极极片中将含有大量的细小颗粒，容易导致对电解液的消耗增加，恶化电池的循环性能，同时大量的细小颗粒存在也会增加负极极片的厚度反弹率。另外，对比例3和对比例4中第二硅氧化物的粒径分布均较窄，这样两种硅氧化物的匹配性会较差，Dn10较小的第二硅氧化物作为填充物填充在Dn10较大的第一硅氧化物间隙中的效果较差，也会增加负极极片的厚度反弹率。
根据上述说明书的揭示和教导，本领域技术人员还可以对上述实施方式进行变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本申请构成任何限制。

Claims (11)

  1. 一种负极活性材料，其特征在于，包括第一硅氧化物以及第二硅氧化物；
    所述第一硅氧化物的粒径Dn10与所述第二硅氧化物的粒径Dn10的比值为8～25，优选为10～20；
    所述第一硅氧化物的粒径Dn10为1.0μm～5.0μm，优选为1.7μm～4.5μm；
    所述第二硅氧化物的粒径Dn10为0.05μm～0.50μm，优选为0.10μm～0.35μm。
  2. 根据权利要求1所述的负极活性材料，其特征在于，所述负极活性材料的粒径Dn10为0.10μm～0.50μm，优选为0.15μm～0.36μm。
  3. 根据权利要求1或2所述的负极活性材料，其特征在于，
    所述第一硅氧化物具有0.8～1.2的粒径分布宽度，优选具有0.9～1.1的粒径分布宽度；
    所述第二硅氧化物具有1.0～1.6的粒径分布宽度，优选具有1.1～1.5的粒径分布宽度；
    其中，所述粒径分布宽度用(Dn90-Dn10)/Dn50表示。
  4. 根据权利要求3所述的负极活性材料，其特征在于，所述负极活性材料具有1.0～1.5的粒径分布宽度，优选具有1.1～1.4的粒径分布宽度。
  5. 根据权利要求1所述的负极活性材料，其特征在于，
    所述第一硅氧化物的粒径Dv50与所述第二硅氧化物的粒径Dv50的比值为1.0～8.0，优选为1.5～7.2；
    所述第一硅氧化物的粒径Dv50为3.0μm～15.0μm，优选为4.4μm～11.0μm；
    所述第二硅氧化物的粒径Dv50为0.4μm～4.0μm，优选为0.9μm～3.5μm。
  6. 根据权利要求1所述的负极活性材料，其特征在于，所述负极活性材料的粒径Dv50为3.5μm～10.5μm，优选为4.0μm～8.5μm。
  7. 根据权利要求1所述的负极活性材料，其特征在于，所述第一硅氧化物的比表面积与所述第二硅氧化物的比表面积的比值为1：(1.5～13.0)，优选为1：(1.8～10.0)。
  8. 根据权利要求1所述的负极活性材料，其特征在于，
    所述第一硅氧化物的比表面积为0.4m 2/g～3.2m 2/g，优选为0.8m 2/g～2.5m 2/g；
    所述第二硅氧化物的比表面积为4.6m 2/g～12.5m 2/g，优选为5.0m 2/g～10.0m 2/g。
  9. 根据权利要求1所述的负极活性材料，其特征在于，所述负极活性材料的比表面积为1.8m 2/g～5.9m 2/g，优选为2.4m 2/g～5.2m 2/g。
  10. 一种电池，包括负极极片，其特征在于，所述负极极片包括根据权利要求1-9中任一项所述的负极活性材料。
  11. 一种装置，其特征在于，包括权利要求10中所述的电池。
PCT/CN2019/125307 2018-12-29 2019-12-13 负极活性材料、电池及装置 WO2020135110A1 (zh)

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