WO2021212418A1 - 负极材料、包含该材料的极片、电化学装置及电子装置 - Google Patents

负极材料、包含该材料的极片、电化学装置及电子装置 Download PDF

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WO2021212418A1
WO2021212418A1 PCT/CN2020/086434 CN2020086434W WO2021212418A1 WO 2021212418 A1 WO2021212418 A1 WO 2021212418A1 CN 2020086434 W CN2020086434 W CN 2020086434W WO 2021212418 A1 WO2021212418 A1 WO 2021212418A1
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negative electrode
silicon
electrode material
silane
carbon
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PCT/CN2020/086434
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English (en)
French (fr)
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姜道义
陈志焕
章婷
崔航
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宁德新能源科技有限公司
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Priority to EP20932519.0A priority Critical patent/EP4141990A4/en
Priority to PCT/CN2020/086434 priority patent/WO2021212418A1/zh
Priority to JP2022563130A priority patent/JP2023525472A/ja
Priority to CN202080099228.4A priority patent/CN115336042A/zh
Publication of WO2021212418A1 publication Critical patent/WO2021212418A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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

  • This application relates to the field of electrochemistry, in particular to a negative electrode material, a pole piece containing the material, an electrochemical device and an electronic device.
  • Lithium-ion batteries have the characteristics of large specific energy, high working voltage, low self-discharge rate, small size, light weight, etc., and have a wide range of applications in the field of consumer electronics. With the rapid development of electric vehicles and portable electronic devices, people have higher and higher requirements for the energy density, safety, and cycle performance of lithium-ion batteries. Among them, silicon-based anode materials have a gram of up to 1500-4200mAh/g. Capacity is considered to be the most promising next-generation lithium-ion anode material.
  • silicon-based anode materials have the following problems: the low electrical conductivity of silicon is about 100 ⁇ .cm, and it has a volume expansion of about 300% during charge and discharge, and there is also unstable SEI (Solid Electrolyte Interphase). Electrolyte interface) membrane, these problems hinder the further application of silicon-based anode materials.
  • the main methods for improving the cycle stability and rate performance of silicon-based materials are as follows: designing porous silicon-based materials, reducing the size of silicon-oxygen materials, coating with oxides, coating with polymers, and coating with carbon materials, etc.
  • the rate performance can be improved to a certain extent, but as the cycle progresses, the occurrence of side reactions and the uncontrollable growth of the SEI film further damage the silicon-based anode
  • the cycle stability of the material; and the coating of oxides and polymers can avoid the coating of electrolyte and electrode materials, but the poor conductivity of silicon-based anode materials will increase the electrochemical impedance, and the inclusion of lithium in the process of deintercalation The coating is easily damaged, which reduces the cycle life of the negative electrode material.
  • the coating of carbon materials can additionally provide excellent conductivity
  • carbon-coated silicon-based materials are likely to be due to Decarburization occurs under the action of repeated shearing force, which affects its Coulomb efficiency.
  • the carbon layer is also easy to peel off from the substrate, accompanied by the SEI film Formation and by-product packaging, electrochemical impedance and polarization increase, thereby affecting the cycle life of lithium-ion batteries.
  • the purpose of this application is to provide a negative electrode material, a pole piece containing the material, an electrochemical device, and an electronic device, so as to improve the cycle stability of the electrochemical device and reduce the volume expansion of the electrochemical device.
  • the specific technical solutions are as follows:
  • the first aspect of the present application provides a negative electrode material, including silicon-based particles and siloxycarbon ceramic material (SiOC) present on the surface of the silicon-based particles, wherein,
  • the atomic ratio of Si, O, and C in the SiOC is 1:0.5 to 5: 0.5 to 10;
  • the Dv50 of the negative electrode material is 2.5 ⁇ m to 10 ⁇ m, and the SiOC accounts for 0.1% to 20% of the mass of the negative electrode material.
  • the SiOC has an amorphous structure.
  • the particle size distribution of the silicon-based particles satisfies: 0.3 ⁇ Dn10/Dv50 ⁇ 0.6.
  • the silicon-based particles include at least one of nano-silicon particles, silicon oxide particles, or carbon-silicon composite particles.
  • the silicon-based particles include at least one of Li element or Mg element.
  • the SiOC is formed by pyrolysis reaction of siloxane raw materials
  • the siloxane raw materials include at least one of siloxane, siloxane hydrolyzate, or silane resin. kind.
  • the siloxane includes methyl triethoxy silane, ethyl triethoxy silane, vinyl triethoxy silane, phenyl triethoxy silane, diphenyl Triethoxysilane, Diethoxymethylphenylsilane, Methyltrimethoxysilane, Benzyltriethoxysilane, Vinyltrimethoxysilane, Isobutyltriethoxysilane, Dimethyl Oxy (methyl) phenyl silane, cyclohexyl methyl dimethoxy silane, octyl trimethoxy silane, propyl trimethoxy silane, octadecyl triethoxy silane, hexyl triethoxy silane , Octylmethyldimethoxysilane, dimethyldiethoxysilane, octadecyltrimethoxysilane, dodecyltriethoxysi
  • the silane resin includes a silicone resin, and the silicone resin includes at least one of an aliphatic group silane resin or a phenylsilane resin.
  • the oxide represented by the chemical formula MeO y on the surface of the silicon-based particles, and the Me element includes at least one of Al, Si, Ti, Mn, V, Cr, Co, or Zr , 0.5 ⁇ y ⁇ 3, the oxide contains a carbon material, wherein the oxide may account for 0.1% to 5% of the mass of the negative electrode material, preferably 1% to 3%.
  • the polymer there is a polymer on the surface of the silicon-based particles, and the polymer contains a carbon material.
  • the polymer may account for 1% to 10% of the mass of the negative electrode material, preferably 3%. % To 6%.
  • the polymer includes polyvinylidene fluoride, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylic acid, polystyrene butadiene rubber, polyacrylamide, At least one of polyimide, polyamideimide, or derivatives of the above substances.
  • the carbon material includes at least one of carbon nanotubes, carbon nanoparticles, carbon fibers, or graphene.
  • the second aspect of the present application provides a negative pole piece, including the negative electrode material as described in the first aspect.
  • the third aspect of the present application provides an electrochemical device, including: a positive pole piece;
  • a separator located between the positive pole piece and the negative pole piece;
  • the negative pole piece is the negative pole piece described in the second aspect.
  • the fourth aspect of the present application provides an electronic device, including the electrochemical device as described in the third aspect.
  • the negative pole piece, electrochemical device and electronic device containing the negative electrode material of the present application have good cycle stability and good volume expansion performance.
  • FIG. 1 is a cross-sectional FIB-TEM structure diagram of a negative electrode material prepared in Example 6 of this application;
  • FIG. 2 is a cross-sectional FIB-TEM structure diagram of the negative electrode material prepared in Comparative Example 1 of the application.
  • a lithium ion battery is used as an example of an electrochemical device to explain the present application, but the electrochemical device of the present application is not limited to a lithium ion battery.
  • the present application provides a negative electrode material, including silicon-based particles and SiOC present on the surface of the silicon-based particles, wherein the atomic ratio of Si, O, and C in the SiOC is 1:0.5 to 5:0.5 to 10.
  • the Dv50 of the negative electrode material is 2.5 ⁇ m to 10 ⁇ m, wherein SiOC accounts for 0.1% to 20% of the mass of the negative electrode material, preferably 0.3% to 10%, and more preferably 0.5% to 5%.
  • the Dv50 indicates that in the particle size distribution on a volume basis, the particle size reaches 50% of the cumulative volume from the small particle size side.
  • the surface cycle stability of the negative electrode material can be significantly improved.
  • the accumulation of by-products is reduced, thereby reducing the volume expansion of the electrochemical device after the cycle.
  • the silicon-based particles may have SiOC present on at least part of the surface, or they may be completely covered by SiOC.
  • the SiOC is an amorphous structure, which is not limited to any theory.
  • the amorphous structure generally has higher mechanical stability, so the negative electrode material of the present application has higher structural stability.
  • the particle size distribution of the silicon-based particles satisfies: 0.3 ⁇ Dn10/Dv50 ⁇ 0.6.
  • the Dn10 indicates a particle size that reaches 10% of the cumulative number from the small particle size side in the particle size distribution on a quantitative basis.
  • the silicon-based particles may include nano-silicon particles, silicon oxide particles, or carbon silicon particles. At least one of composite particles.
  • the silicon-based particles include at least one of Li or Mg.
  • the inventors have found that SiOC exists on the surface of silicon-based particles containing Li and/or Mg, and can also Effectively improve the cycle performance of electrochemical devices.
  • the SiOC is formed from a siloxane raw material through a pyrolysis reaction, wherein the siloxane raw material includes at least one of siloxane, siloxane hydrolyzate, or silane resin .
  • the siloxane may include methyl triethoxy silane, ethyl triethoxy silane, vinyl triethoxy silane, phenyl triethoxy silane, diphenyl Triethoxysilane, Diethoxymethylphenylsilane, Methyltrimethoxysilane, Benzyltriethoxysilane, Vinyltrimethoxysilane, Isobutyltriethoxysilane, Dimethyl Oxy (methyl) phenyl silane, cyclohexyl methyl dimethoxy silane, octyl trimethoxy silane, propyl trimethoxy silane, octadecyl triethoxy silane, hexyl triethoxy silane , Octylmethyldimethoxysilane, dimethyldiethoxysilane, octadecyltrimethoxysilane, dodecyltriethoxys
  • the silane resin includes a silicone resin
  • the silicone resin includes at least one of an aliphatic group silane resin or a phenylsilane resin
  • the aliphatic group silane resin may include polydimethylsiloxane, methyl At least one of hydrogen-based silicone resin or vinyl methyl silicone resin
  • the phenyl silane resin may include at least one of polydiphenyl silicone resin, polymethyl phenyl silicone resin, or vinyl phenyl silicone resin.
  • the silicon-based particles there is an oxide represented by the chemical formula MeO y on the surface of the silicon-based particles, and the Me element includes at least one of Al, Si, Ti, Mn, V, Cr, Co or Zr, 0.5 ⁇ y ⁇ 3, it should be noted that the silicon-based particles may have oxides on at least part of the surface, or they may be all covered by oxides.
  • the content of oxides is not particularly limited.
  • the oxides may account for 0.1% to 5% of the mass of the negative electrode material, preferably 1% to 3%.
  • the inventor’s research found that, without being limited to any theory, when oxides exist on the surface of SiOC-containing silicon-based particles, the oxide itself is stable, so when the oxide is further encapsulated in SiOC, the negative electrode material can have better structural stability And, the oxide may contain a carbon material, thereby further improving the conductivity of the negative electrode material.
  • the silicon-based particle there is a polymer on the surface of the silicon-based particle, and the polymer contains a carbon material.
  • the silicon-based particle may have a polymer on at least part of the surface, for example, It can be all wrapped by polymer.
  • the content of the polymer is not particularly limited.
  • the polymer may account for 1% to 10% of the mass of the negative electrode material, preferably 3% to 6%.
  • the polymer itself generally has good structural stability and can also be used as a carrier for conductive materials such as carbon materials.
  • Conductive polymer may also be present on the surface of silicon-based particles containing SiOC.
  • the carbon material may include at least one of carbon nanotubes, carbon nanoparticles, carbon fibers, or graphene.
  • the amount of carbon material is not particularly limited, and can be selected according to common knowledge in the art.
  • the above-mentioned carbon materials may be used singly or in combination of two or more in any ratio.
  • the addition amount of carbon materials in the oxide ranges from 10% to 90%, for example: the addition amount of carbon materials in the oxide is 10%; the addition of carbon materials in the oxide The amount of carbon material is 20%; the amount of carbon material in the oxide is 30%; the amount of carbon material in the oxide is 40%; the amount of carbon material in the oxide is 50%; the carbon material is in the oxide The addition amount of carbon material is 60%; the addition amount of carbon material in the oxide is 70%; the addition amount of carbon material in the oxide is 80%; the addition amount of carbon material in the oxide is 90%.
  • the addition amount of carbon materials in the polymer ranges from 20% to 80%, for example, the addition amount of carbon materials in the polymer is 20%; the addition of carbon materials in the polymer The amount of carbon materials is 30%; the amount of carbon materials added to the polymer is 40%; the amount of carbon materials added to the polymer is 50%; the amount of carbon materials added to the polymer is 60%; the amount of carbon materials added to the polymer is 60%.
  • the addition amount of carbon material is 70%; the addition amount of carbon material in the polymer is 80%.
  • the polymer includes polyvinylidene fluoride, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylic acid, polystyrene butadiene rubber, polyacrylamide, poly At least one of imide, polyamideimide, or derivatives of the above substances.
  • SiOC and the silicon-based particles have good bonding strength, so that the surface cycle stability of the negative electrode material during the volume expansion and contraction process is significantly improved, thereby reducing by-products accumulation.
  • the preparation method of the negative electrode material provided in this application is not particularly limited.
  • it can be prepared by the following method:
  • the precursor is sintered in an inert gas, and after heat preservation, a negative electrode material is obtained.
  • the application has no special restrictions on the organic solvent, as long as it can achieve the purpose of the invention.
  • the organic solvent may include at least one of n-hexane and ethanol.
  • the water content of the aqueous organic solvent is 5 to 10 Vol%.
  • the application has no special restrictions on the catalyst, as long as it can achieve the purpose of the invention of the application.
  • the catalyst may be an organic acid solution, such as an oxalic acid solution.
  • the stirring time is 0.5 to 24 hours.
  • At least one method of rotary evaporation, spray drying, filtration, or freeze drying may be used to remove the solvent.
  • the sintering temperature is 600 to 1000°C
  • the holding time is 2 to 12 hours
  • the heating rate is 3 to 20°C/min.
  • the inert gas may be at least one of nitrogen, argon, or helium.
  • the surface of the silicon-based particles contains abundant active groups such as silanol, and the siloxane raw material is hydrolyzed
  • the silica gel particles are also rich in silanol.
  • the two are dehydrated and cond
  • the surface cycle stability can be significantly improved, and the accumulation of by-products can be reduced, so that the volume expansion of the electrochemical device after the cycle is reduced; on the other hand, the SiOC can be effectively adjusted by adjusting the composition of the precursor and the sintering temperature.
  • the characteristic of lithium insertion thereby effectively increasing the speed of lithium insertion, reducing the polarization of the negative electrode of the electrochemical device, thereby reducing the impedance.
  • This application also provides a negative electrode sheet, which includes the negative electrode material described in any of the above embodiments.
  • the surface cycle stability of the negative electrode material is significantly improved during the volume expansion and contraction process, thereby reducing the accumulation of by-products.
  • the negative pole piece has good cycle stability and good volume expansion performance.
  • the present application also provides an electrochemical device, including: a positive pole piece, a negative pole piece, a separator, and an electrolyte, the separator is located between the positive pole piece and the negative pole piece, wherein the electrochemical
  • the device contains the negative pole piece described in the embodiments of the present application. Because the negative electrode material in the negative pole piece significantly improves the surface cycle stability during the volume expansion and contraction process, thereby reducing the accumulation of by-products, the electrochemical device of the present application It has good cycle stability and good volume expansion performance.
  • a secondary battery can be manufactured by the following process: overlap the positive electrode and the negative electrode via spacers, and place them in the battery container after winding, folding and other operations as needed, and inject the electrolyte into the battery container and seal it.
  • the negative electrode used is The above-mentioned negative pole piece provided in this application.
  • an overcurrent prevention element, a guide plate, etc. can also be placed in the battery container as needed, so as to prevent the internal pressure of the battery from rising and overcharging and discharging.
  • the present application also provides an electronic device, including the electrochemical device described in the embodiments of the present application. Since the electrochemical device contained in the electronic device has good cycle stability and good volume expansion performance, it has a higher Long life and safety.
  • the positive pole piece in this application is not particularly limited, and any positive pole piece known in the art can be used.
  • a positive pole piece containing lithium cobaltate, a positive pole piece containing lithium manganate, a positive pole piece containing lithium iron phosphate, or a positive pole piece containing lithium nickel cobalt manganate or lithium nickel cobalt aluminate is not particularly limited, and any positive pole piece known in the art.
  • a positive pole piece containing lithium cobaltate a positive pole piece containing lithium manganate, a positive pole piece containing lithium iron phosphate, or a positive pole piece containing lithium nickel cobalt manganate or lithium nickel cobalt aluminate.
  • the electrolyte is not particularly limited, and any electrolyte known in the art can be used, for example, it can be any of a gel state, a solid state, and a liquid state.
  • the liquid electrolyte solution can include lithium salt and non-aqueous. Solvent.
  • the lithium salt is not particularly limited, and any lithium salt known in the art can be used as long as the purpose of the application can be achieved.
  • the lithium salt may include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 At least one of CF 3 ) 3 or LiPO 2 F 2.
  • LiPF 6 can be used as the lithium salt.
  • the non-aqueous solvent is not particularly limited as long as it can achieve the purpose of the present application.
  • the non-aqueous solvent may include at least one of carbonate compounds, carboxylate compounds, ether compounds, nitrile compounds, or other organic solvents.
  • the carbonate compound may include diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC), methyl ethyl carbonate Ester (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), carbonic acid 1 ,2-Difluoroethylene, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1 -Fluoro-2-methylethylene, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluorocarbonate- At least one of 2-methylethylene or trifluoromethylethylene carbonate.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • DPC dipropy
  • the material of the current collector of the present application is not particularly limited, and materials well known to those skilled in the art can be used.
  • the material of the current collector may include, but is not limited to: copper, nickel, titanium, molybdenum, aluminum, iron, zinc, or stainless steel.
  • silica material Disperse 100g of silica material in 500mL of water-containing n-hexane and stir evenly.
  • the silica material is SiO (silicon monoxide) and the water content of n-hexane is 5Vol%;
  • step 3 Add the catalyst to the mixed solution obtained in step 2 according to 1/10 of the added amount of SiO. After heating to 60°C and stirring for 2 hours, remove the solvent and dry to obtain the precursor, wherein the catalyst has a concentration of 2.5mol/L ⁇ oxalic acid solution;
  • step 4 The precursor obtained in step 3 is sintered in argon gas, the sintering temperature is 600° C., the holding time is 2 hours, and the heating rate is 3° C./min to obtain the negative electrode material.
  • siloxane raw material is BSB (1,4-bis(triethoxysilyl)benzene), the rest is the same as in Example 1.
  • the silicon-oxygen material is a lithium-containing silicon-oxygen material
  • the rest is the same as in Example 6, and lithium accounts for 8% of the mass of the above-mentioned lithium-containing silicon-oxygen material.
  • the silicon-oxygen material is a magnesium-containing silicon-oxygen material
  • the rest is the same as in Example 6, and magnesium accounts for 13% of the mass of the above-mentioned magnesium-containing silicon-oxygen material.
  • silica material Disperse 100g of silica material in 500mL of water-containing n-hexane and stir evenly.
  • the silica material is SiO (silicon monoxide) and the water content of n-hexane is 5Vol%;
  • step 2 After removing the solvent and drying the mixed solution obtained in step 1, it is sintered in an inert gas at a sintering temperature of 600° C., holding for 2 hours, and a heating rate of 3° C./min to obtain a negative electrode material.
  • the silicon-oxygen material is a lithium-containing silicon-oxygen material
  • the rest is the same as Comparative Example 1, and lithium accounts for 8% of the mass of the above-mentioned lithium-containing silicon-oxygen material.
  • the silicon-oxygen material is a magnesium-containing silicon-oxygen material
  • the rest is the same as Comparative Example 1, and magnesium accounts for 13% of the mass of the above-mentioned magnesium-containing silicon-oxygen material.
  • the lithium-containing silicon-oxygen material may be a pre-inserted lithium material of SiO, and lithium accounts for 6% to 12% of the mass of the lithium-containing silicon-oxygen material;
  • the magnesium-containing silicon-oxygen material may be a pre-inserted magnesium material of SiO, and magnesium accounts for the magnesium-containing silicon-oxygen material 5% to 20% of the quality.
  • Observation of powder particle micro-morphology Use scanning electron microscope to observe the powder micro-morphology of the negative electrode material to characterize the surface coating of the material.
  • the selected test instrument is: OXFORD EDS (X-max-20mm2), and the acceleration voltage is 10KV to adjust the focus.
  • the observation magnification is from 50K for high magnification observation, and for low magnification, 500-2000 is mainly used to observe particle agglomeration.
  • the adsorption amount of the sample monolayer is calculated based on the Brownauer-Ett-Taylor adsorption theory and its formula (BET formula), thereby calculating The specific surface area of the solid.
  • the negative electrode material sample is heated and burned by a high-frequency furnace under oxygen-rich conditions to oxidize carbon and sulfur into carbon dioxide and sulfur dioxide. After treatment, the gas enters the corresponding absorption pool, absorbs the corresponding infrared radiation, and then converts it into a detector. Corresponding signal. This signal is sampled by the computer, after linear correction, it is converted into a value proportional to the concentration of carbon dioxide and sulfur dioxide, and then the value of the entire analysis process is accumulated. After the analysis is completed, the accumulated value is divided by the weight value in the computer, and then multiplied by Correction coefficient, deduct blank, you can get the percentage of carbon and sulfur in the sample.
  • a high-frequency infrared carbon and sulfur analyzer (Model: Shanghai Dekai HCS-140) was used for sample testing.
  • FIG. 1 is a cross-sectional FIB-TEM structure diagram of the negative electrode material prepared in Example 6.
  • a clear SiOC layer structure can be seen from the figure, and the thickness of the SiOC layer is about 4 nm.
  • Figure 2 is a cross-sectional FIB-TEM structure diagram of the negative electrode material prepared in Comparative Example 1. The SiOC layer structure cannot be seen from the figure.
  • XRD test Weigh 1.0-2.0g of the negative electrode material sample into the groove of the glass sample holder, and use a glass sheet to compact and smooth it, using an X-ray diffractometer (model Brook, D8) according to JJS K 0131-1996 "General Principles of X-ray Diffraction Analysis" to test, the test voltage is set to 40kV, the current is 30mA, the scanning angle range is 10-85°, the scanning step is 0.0167°, and the time set for each step is 0.24s to get XRD In the diffraction pattern, the highest intensity value I1 of 2 ⁇ attributable to 28.4° and the highest intensity I2 attributable to 21.0° are obtained from the figure, so as to calculate the ratio of I2/I1.
  • the negative electrode material prepared in each example and comparative example was mixed with conductive carbon black and polymer in a ratio of 80:10:10, added deionized water and stirred to form a slurry, and a scraper was used to coat the surface of the current collector with a thickness of 100 ⁇ m Coating, after being dried in a vacuum drying oven for 12 hours at 85°C, it is cut into a disc with a diameter of 1cm in a dry environment by a punching machine, a metal lithium sheet is used as the counter electrode in the glove box, and the isolation membrane is selected as ceglard composite Membrane, add electrolyte to assemble button battery, use LAND series battery test test to charge and discharge the battery, the first efficiency calculation method is, discharge cut-off voltage is 2.0V capacity/charge voltage cut-off to 0.005V corresponding
  • Table 1 The test results are shown in Table 1.
  • the half-cell discharge cut-off voltage is the gram capacity corresponding to 2.0V.
  • the test temperature is 25°C or 45°C
  • the battery is charged to 4.4V at a constant current of 0.7C, charged to 0.025C at a constant voltage, and discharged to 3.0V at 0.5C after standing for 5 minutes.
  • the capacity obtained in this step is the initial capacity
  • the 0.7C charge/0.5C discharge is carried out for a cycle test, and the capacity at each step is used as the ratio of the initial capacity to obtain the capacity decay curve.
  • the number of cycles with a cut-off capacity retention rate of 90% at 25°C is recorded as the room temperature cycle performance of the battery, and the number of cycles with a cut-off capacity retention rate of 80% at 45°C is recorded as the high temperature cycle performance of the battery.
  • LiCoO 2 , conductive carbon black and polyvinylidene fluoride (PVDF) were mixed thoroughly in the N-methylpyrrolidone solvent system at a weight ratio of 95%:2.5%:2.5% to obtain a solid content of 75wt% Positive electrode slurry.
  • the prepared positive electrode slurry was coated on the positive electrode current collector aluminum foil, dried, and cold pressed to obtain a positive electrode with a coating thickness of 110 ⁇ m.
  • the graphite, the negative electrode material prepared according to the embodiment and the comparative example, the conductive agent and the binder were mixed in a weight ratio of 70%: 15%: 5%: 10%, and an appropriate amount of water was added, and the solid content was 55wt% to 70wt%. Knead at 5%, then add an appropriate amount of water to adjust the viscosity of the slurry to 4000 to 6000 Pa ⁇ s to make a negative electrode slurry.
  • the prepared negative electrode slurry is coated on the negative electrode current collector copper foil, dried and cooled Press to obtain a negative electrode with a coating thickness of 100 ⁇ m.
  • conductive carbon black is used as the conductive agent
  • PAA polyacrylic acid
  • LiPF 6 In a dry argon atmosphere, add LiPF 6 to a solvent mixed with propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC), and mix well, then add 12.5% by weight of fluorine Substitute ethylene carbonate (FEC) and mix well to obtain electrolyte.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • FEC fluorine Substitute ethylene carbonate
  • the weight ratio of propylene carbonate, ethylene carbonate, and diethyl carbonate is 1:1:1, and the concentration of LiPF 6 is 1.15 mol/L.
  • a polyethylene (PE) porous polymer film with a thickness of 15 ⁇ m is used as the separator.
  • the electrode assembly is wound by winding, and the electrode assembly is placed in the outer package, electrolyte is injected, packaged, and chemically formed. , Degassing, trimming and other processes to obtain lithium-ion batteries.
  • Example 7 After comparing Example 7 with Comparative Example 1, it can be seen that the number of cycles at 25°C is slightly greater than that of Comparative Example 1, and the number of cycles at 45°C is slightly smaller than that of Comparative Example 1, but the expansion rate and discharge rate are significantly improved. This may be due to the addition of PDMS Due to the poor tiling performance of PDMS itself on the surface of the negative electrode material, more PDMS addition is more likely to cause surface instability, which will affect the cycle performance of lithium-ion batteries, but it will affect the cycle performance of lithium-ion batteries. Both the expansion rate and the discharge rate can be improved.
  • Example 10 shows that in the case of the same Li-containing siloxane material, the negative electrode material with SiOC on the surface is compared with the negative electrode material without SiOC on the surface, and the lithium ion battery cycles at different temperatures.
  • the performance is significantly improved, and the expansion rate and discharge rate performance are also improved.
  • Example 11 shows that in the case of the same Mg-containing siloxane material, the negative electrode material with SiOC on the surface is compared with the negative electrode material without SiOC on the surface, and the lithium ion battery cycles at different temperatures.
  • the performance is significantly improved, and the expansion rate and discharge rate performance are also improved.
  • Examples 7 to 9 and Comparative Example 1 show that the negative electrode material with SiOC on the surface is prepared by adding different content of siloxane materials. Compared with the negative electrode material without SiOC on the surface, the cycle performance of the lithium ion battery is significantly improved, and the expansion rate is lower. The discharge rate performance is also improved.

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Abstract

本申请提供了一种负极材料、包含该材料的极片、电化学装置及电子装置，其中负极材料，包括硅基颗粒及存在于该硅基颗粒表面的SiOC，SiOC中Si、O、C的原子比为1：0.5至5：0.5至10。本申请能够使负极材料在体积膨胀收缩的过程中表面循环稳定性得到显著改善，从而减少副产物堆积，从而使使用该负极极片的电化学装置具有良好的循环稳定性和良好的体积膨胀性能。

Description

负极材料、包含该材料的极片、电化学装置及电子装置 技术领域
本申请涉及电化学领域，具体涉及一种负极材料、包含该材料的极片、电化学装置及电子装置。
背景技术
锂离子电池具有比能量大、工作电压高、自放电率低、体积小、重量轻等特点，在消费电子领域具有广泛的应用。随着电动汽车和可移动电子设备的高速发展，人们对锂离子电池的能量密度、安全性、循环性能等相关要求越来越高，其中，硅基负极材料具有高达1500～4200mAh/g的克容量，被认为是最具有应用前景的下一代锂离子负极材料。
但是硅基负极材料存在以下问题：硅的低电导性较低，为100Ω.cm左右，其在充放电过程中具有约300％的体积膨胀，并且还存在不稳定的SEI(Solid Electrolyte Interphase，固体电解质界面)膜，这些问题阻碍了硅基负极材料的进一步应用。目前提升硅基材料的循环稳定和倍率性能主要有以下手段：设计多孔硅基材料、降低硅氧材料的尺寸、采用氧化物包覆、聚合物包覆以及碳材料包覆等。对于设计多孔硅基材料和降低硅氧材料的尺寸的手段，能够一定程度上可以改善倍率性能，但随着循环的进行，副反应的发生以及不可控的SEI膜的生长进一步破坏了硅基负极材料的循环稳定性；而氧化物和聚合物的包覆可以避免电解液和电极材料的包覆，但由于硅基负极材料较差的导电会增加电化学阻抗，且在脱嵌锂过程中包覆层易被破坏，从而使负极材料循环寿命下降；虽然碳材料的包覆可以附加提供优异的导电性，但是在锂离子电池极片加工过程中，一方面碳包覆硅基材料很可能由于反复剪切力的作用出现脱碳现象，从而影响其库伦效率，另一方面，在多次的循环过程中由于硅的膨胀收缩和破裂，碳层也易于从基体上剥落，伴随着SEI膜的生成以及副产物的包裹，电化学阻抗和极化增大，从而影响锂离子电池的循环寿命。
因此，亟需一种能够进一步提高锂离子电池循环稳定性和降低锂离子电池体积膨胀的硅基负极材料。
发明内容
本申请的目的在于提供一种负极材料、包含该材料的极片、电化学装置及电子装置，以提高电化学装置循环稳定性、降低电化学装置的体积膨胀。具体技术方案如下：
本申请的第一方面提供了一种负极材料，包括硅基颗粒及存在于该硅基颗粒表面的硅氧碳陶瓷材料(SiOC)，其中，
所述SiOC中Si、O、C的原子比为1：0.5至5：0.5至10；
所述负极材料的Dv50为2.5μm至10μm，所述SiOC占负极材料质量的0.1％至20％。
在本申请的一种实施方案中，所述SiOC为无定形结构。
在本申请的一种实施方案中，所述硅基颗粒的粒径分布满足：0.3≤Dn10/Dv50≤0.6。
在本申请的一种实施方案中，所述硅基颗粒包括纳米硅颗粒、氧化亚硅颗粒或碳硅复合颗粒中的至少一种。
在本申请的一种实施方案中，所述硅基颗粒中包括Li元素或Mg元素中的至少一种。
在本申请的一种实施方案中，所述SiOC是由硅氧烷原料经热解反应而形成的，所述硅氧烷原料包括硅氧烷、硅氧烷水解产物或硅烷树脂中的至少一种。
在本申请的一种实施方案中，所述硅氧烷包括甲基三乙氧基硅烷，乙基三乙氧基硅烷，乙烯基三乙氧基硅烷，苯基三乙氧基硅烷，二苯基三乙氧基硅烷，二乙氧基甲基苯基硅烷，甲基三甲氧基硅烷，苄基三乙氧基硅烷，乙烯基三甲氧基硅烷，异丁基三乙氧基硅烷，二甲氧基(甲基)苯基硅烷，环己基甲基二甲氧基硅烷，辛基三甲氧基硅烷，丙基三甲氧基硅烷，十八烷基三乙氧基硅烷，己基三乙氧基硅烷，辛基甲基二甲氧基硅烷，二甲基二乙氧基硅烷，十八烷基三甲氧基硅烷，十二烷基三乙氧基硅烷，烯丙基三甲氧基硅烷，十六烷基三甲氧基硅烷，甲基乙烯基二乙氧基硅烷，正辛基三乙氧基硅烷，二异丁基二甲氧基硅烷，(氯甲基)二乙氧基(甲基)硅烷，二甲氧基甲基乙烯基硅烷，γ-氨丙基甲基二乙氧基硅烷或1,4-双(三乙氧基甲硅烷基) 苯中的至少一种；
所述硅烷树脂包含有机硅树脂，所述有机硅树脂包括脂肪族基团硅烷树脂或苯基硅烷树脂中的至少一种。
在本申请的一种实施方案中，所述硅基颗粒的表面还存在化学式MeO y代表的氧化物，Me元素包括Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种，0.5≤y≤3，所述氧化物中包含碳材料，其中，氧化物可以占负极材料质量的0.1％至5％，优选为1％至3％。
在本申请的一种实施方案中，所述硅基颗粒的表面还存在聚合物，所述聚合物中包含碳材料，其中，聚合物可以占负极材料质量的1％至10％，优选为3％至6％。
在本申请的一种实施方案中，所述聚合物包括聚偏氟乙烯、羧甲基纤维素、羧甲基纤维素钠、聚乙烯基吡咯烷酮、聚丙烯酸、聚丁苯橡胶、聚丙烯酰胺、聚酰亚胺、聚酰胺酰亚胺或上述物质衍生物中的至少一种。
在本申请的一种实施方案中，所述碳材料包括碳纳米管、碳纳米颗粒、碳纤维或石墨烯中的至少一种。
本申请的第二方面提供了一种负极极片，包括如上述第一方面所述的负极材料。
本申请的第三方面提供了一种电化学装置，包括：正极极片；
负极极片；
隔膜，所述隔膜位于所述正极极片和所述负极极片之间；以及
电解液；
其中，所述负极极片为上述第二方面所述的负极极片。
本申请的第四方面提供了一种电子装置，包括如上述第三方面所述的电化学装置。
使用本申请提供的负极材料，由于硅基颗粒表面存在SiOC，SiOC与硅基颗粒具有良好的结合强度，使负极材料在体积膨胀收缩的过程中表面循环稳定性得到显著改善，从而减少副产物堆积，并且，包含本申请负极材料的负极极片、电化学装置及电子装置具有良好的循环稳定性和良好的体积膨胀性能。
附图说明
为了更清楚地说明本申请和现有技术的技术方案，下面对实施例和现有技术中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的技术方案。
图1为本申请实施例6制得的负极材料的截面FIB-TEM结构图；
图2为本申请对比例1制得的负极材料的截面FIB-TEM结构图。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照附图和实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他技术方案，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
本申请提供了一种负极材料，包括硅基颗粒及存在于该硅基颗粒表面的SiOC，其中，所述SiOC中Si、O、C的原子比为1：0.5至5：0.5至10，所述负极材料的Dv50为2.5μm至10μm，其中，SiOC占负极材料质量的0.1％至20％，优选为0.3％至10％，进一步优选为0.5％至5％。
其中，所述Dv50表示颗粒在体积基准的粒度分布中，从小粒径侧起，达到体积累积50％的粒径。
发明人研究发现，由于硅基颗粒的表面存在SiOC，使得SiOC与硅基颗粒具有良好的结合强度，进而使负极材料稳定，在体积膨胀收缩的过程中，能够显著改善负极材料表面循环稳定性，减少副产物堆积，从而减少电化学装置在循环后的体积膨胀，需要说明的是，硅基颗粒可以是至少部分表面存在SiOC，也可以是全部被SiOC包裹。
本申请的一种实施方案中，所述SiOC为无定形结构，不限于任何理论，无定形结构通常具有更高的力学稳定性，因而本申请的负极材料结构稳定性更高。
本申请的一种实施方案中，所述硅基颗粒的粒径分布满足：0.3≤Dn10/Dv50≤0.6。
其中，所述Dn10表示在数量基准的粒度分布中，从小粒径侧起，达到数量累积10％的粒径。
本申请对硅基颗粒没有特别的限制，只要能达到本申请的发明目的即可，在本申请的一种实施方案中，所述硅基颗粒可以包括纳米硅颗粒、氧化亚硅颗粒或碳硅复合颗粒中的至少一种。
本申请的一种实施方案中，所述硅基颗粒中包括Li或Mg元素中的至少一种，发明人研究发现，SiOC存在于含有Li元素和/或Mg元素的硅基颗粒表面，亦能够有效提高电化学装置的循环性能。
本申请的一种实施方案中，所述SiOC是由硅氧烷原料经热解反应而形成的，其中，硅氧烷原料包括硅氧烷、硅氧烷水解产物或硅烷树脂中的至少一种。
本申请的一种实施方案中，所述硅氧烷可以包括甲基三乙氧基硅烷，乙基三乙氧基硅烷，乙烯基三乙氧基硅烷，苯基三乙氧基硅烷，二苯基三乙氧基硅烷，二乙氧基甲基苯基硅烷，甲基三甲氧基硅烷，苄基三乙氧基硅烷，乙烯基三甲氧基硅烷，异丁基三乙氧基硅烷，二甲氧基(甲基)苯基硅烷，环己基甲基二甲氧基硅烷，辛基三甲氧基硅烷，丙基三甲氧基硅烷，十八烷基三乙氧基硅烷，己基三乙氧基硅烷，辛基甲基二甲氧基硅烷，二甲基二乙氧基硅烷，十八烷基三甲氧基硅烷，十二烷基三乙氧基硅烷，烯丙基三甲氧基硅烷，十六烷基三甲氧基硅烷，甲基乙烯基二乙氧基硅烷，正辛基三乙氧基硅烷，二异丁基二甲氧基硅烷，(氯甲基)二乙氧基(甲基)硅烷，二甲氧基甲基乙烯基硅烷，γ-氨丙基甲基二乙氧基硅烷或1,4-双(三乙氧基甲硅烷基)苯中的至少一种。
所述硅烷树脂包含有机硅树脂，所述有机硅树脂包括脂肪族基团硅烷树脂或苯基硅烷树脂中的至少一种，其中，脂肪族基团硅烷树脂可以包括聚二甲硅氧烷、甲基氢硅树脂或乙烯基甲基硅树脂中的至少一种，苯基硅烷树脂可以包括聚二苯基硅树脂、聚甲基苯基硅树脂或乙烯基苯基硅树脂中的至少一种。
本申请的一种实施方案中，所述硅基颗粒的表面还存在化学式MeO y代表的氧化物，Me元素包括Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种，0.5≤y≤3，需要说明的是，硅基颗粒可以至少部分表面存在氧化物，也可以是全部被氧化物包裹。在本申请中，对氧化物的含量不做特殊的限定，例如可以是氧化物占负极材料质量的0.1％至5％，优选为1％至3％。
发明人研究发现，不限于任何理论，含有SiOC的硅基颗粒表面存在氧化物时，由于氧化物本身具有稳定性，因此在氧化物进一步包裹SiOC时，能够使负极材料具有更好的结构稳定性，并且，所述氧化物中可以包含碳材料，从而进一步提高负极材料的导电性。
本申请的一种实施方案中，所述硅基颗粒的表面还存在聚合物，所述聚合物中包含碳材料，需要说明的是，硅基颗粒可以至少部分表面存在聚合物，例如可以是也可以是全部被聚合物包裹。在本申请中，对聚合物的含量不做特殊的限定，例如可以是聚合物占负极材料质量的1％至10％，优选为3％至6％。
发明人研究发现，不限于任何理论，聚合物自身通常具有良好的结构稳定性，并且还能作为导电物质如碳材料的载体，为了进一步提高负极材料的导电性，在本申请的一种实施方案中，含有SiOC的硅基颗粒表面还可以存在导电聚合物。
本申请对所述碳材料没有特别限制，只要能达到本申请的发明目的即可。在本申请的一种实施方案中，所述碳材料可以包括碳纳米管、碳纳米颗粒、碳纤维或石墨烯中的至少一种。碳材料的用量没有特别限制，可以根据本领域公知常识进行选择。上述碳材料可以单独使用一种，也可以将两种以上以任意比例组合使用。
本申请对碳材料在氧化物或聚合物中的添加量没有特别限制，只要能达到本申请的发明目的即可。在本申请的一种实施方案中，碳材料在氧化物中的添加量范围为10％至90％，例如：碳材料在氧化物中的添加量为10％；碳材料在氧化物中的添加量为20％；碳材料在氧化物中的添加量为30％；碳材料在氧化物中的添加量为40％；碳材料在氧化物中的添加量为50％；碳材料在氧化物中的添加量为60％；碳材料在氧化物中的添加量为70％；碳材料在 氧化物中的添加量为80％；碳材料在氧化物中的添加量为90％。
在本申请的一种实施方案中，碳材料在聚合物中的添加量范围为20％至80％，例如，碳材料在聚合物中的添加量为20％；碳材料在聚合物中的添加量为30％；碳材料在聚合物中的添加量为40％；碳材料在聚合物中的添加量为50％；碳材料在聚合物中的添加量为60％；碳材料在聚合物中的添加量为70％；碳材料在聚合物中的添加量为80％。
本申请的一种实施方案中，所述聚合物包括聚偏氟乙烯、羧甲基纤维素、羧甲基纤维素钠、聚乙烯基吡咯烷酮、聚丙烯酸、聚丁苯橡胶、聚丙烯酰胺、聚酰亚胺、聚酰胺酰亚胺或上述物质衍生物中的至少一种。
本申请提供的一种负极材料，由于硅基颗粒表面存在SiOC，SiOC与硅基颗粒具有良好的结合强度，使负极材料在体积膨胀收缩的过程中表面循环稳定性得到显著改善，从而减少副产物堆积。
本申请所提供的负极材料的制备方法没有特别限制，例如可以通过以下方法制备：
1、将硅氧烷原料溶于含水有机溶剂中，得到溶液A；
2、将催化剂溶液加入溶液A中，得到溶液B；
3、将硅基颗粒加入溶液B，搅拌并去除溶剂，烘干后得到前驱体；
4、将前驱体在惰性气体中烧结，经保温后，得到负极材料。
或者，可以通过以下方法制备：
先将硅基颗粒分散于含水有机溶剂中得到混合液C，然后将硅氧烷原料加入混合液C，再加入催化剂，搅拌并去除溶剂，烘干后得到前驱体，然后将前驱体在惰性气体中烧结，经保温后，得到负极材料。
本申请对有机溶剂没有特别限制，只要能达到本申请的发明目的即可，在本申请的一种实施方案中，所述有机溶剂可以包含正己烷、乙醇中的至少一种。
本申请的一种实施方案中，含水有机溶剂的含水量为5至10Vol％。
本申请对催化剂没有特别限制，只要能达到本申请的发明目的即可，在本申请的一种实施方案中，所述催化剂可以为有机酸溶液，例如草酸溶液。
本申请的一种实施方案中，搅拌时间为拌0.5至24h。
本申请的一种实施方案中，可以采用旋转蒸发、喷雾干燥、过滤、或冷冻干燥的至少一种方式去除溶剂。
本申请的一种实施方案中，烧结温度为600至1000℃，保温时间2至12h，升温速率为3至20℃/min。
本申请的一种实施方案中，惰性气体可以采用氮气、氩气或者氦气中的至少一种。
本申请在制备负极材料的过程中，一方面，通过将硅氧烷原料和硅基颗粒在含水溶剂中混合，硅基颗粒表面含有丰富的硅羟基等活性基团，而硅氧烷原料水解后的硅胶粒子也含有丰富的硅羟基，二者在水溶液中脱水缩合形成化学结合力强的前驱体，从而在烧结后，使SiOC与硅基颗粒具有较好的结合强度，从而使得负极材料在体积膨胀收缩的过程中，能够显著改善表面循环稳定性，减少副产物堆积从而使得循环后电化学装置的体积膨胀降低；另一方面，可以通过调节前驱体的组分和烧结温度，能够有效调节SiOC的嵌锂特性，从而有效提升嵌锂速度，降低电化学装置负极极化，从而降低阻抗。
本申请还提供了一种负极极片，包括上述任一实施方案中所述的负极材料，由于负极材料在体积膨胀收缩的过程中表面循环稳定性显著改善，从而减少副产物堆积，本申请的负极极片具有良好的循环稳定性和良好的体积膨胀性能。
本申请还提供了一种电化学装置，包括：正极极片，负极极片，隔膜，以及电解液，所述隔膜位于所述正极极片和所述负极极片之间，其中，该电化学装置为包含本申请实施方案中所述的负极极片，由于负极极片中的负极材料在体积膨胀收缩的过程中表面循环稳定性显著改善，从而减少副产物堆积，因此本申请的电化学装置具有良好的循环稳定性和良好的体积膨胀性能。
电化学装置的制备过程为本领域技术人员所熟识的，本申请没有特别的限制。例如二次电池可以通过以下过程制造：将正极和负极经由间隔件重叠，并根据需要将其卷绕、折叠等操作后放入电池容器，将电解液注入电池容器并封口，其中所用的负极为本申请提供的上述负极极片。此外，也可以根据需要将防过电流元件、导板等置于电池容器中，从而防止电池内部的压力上升、过充放电。
本申请还提供了一种电子装置，包含本申请实施方案中所述的电化学装置，由于该电子装置中包含的电化学装置具有良好的循环稳定性和良好的体积膨胀性能，因此具有更高的使用寿命和安全性。
本申请中的正极极片没有特别限制，可以采用本领域公知的任何正极极片。例如，含有钴酸锂的正极极片，含有锰酸锂的正极极片，含有磷酸铁锂的正极极片，或含有镍钴锰酸锂或镍钴铝酸锂的正极极片。
本申请中，所述电解液没有特别限制，可以使用本领域公知的任何电解液，例如可以是凝胶态、固态和液态中的任一种，例如，液态电解液可以包括锂盐和非水溶剂。
锂盐没有特别限制，可以使用本领域公知的任何锂盐，只要能实现本申请的目的即可。例如，锂盐可以包括LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3或LiPO 2F 2中的至少一种。例如，锂盐可选用LiPF 6。
非水溶剂没有特别限定，只要能实现本申请的目的即可。例如，非水溶剂可以包括碳酸酯化合物、羧酸酯化合物、醚化合物、腈化合物或其它有机溶剂中的至少一种。
例如，碳酸酯化合物可以包括碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)、碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)、碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯或碳酸三氟甲基亚乙酯中的至少一种。
本申请的集流体的材料没有特别限制，可以采用本领域技术人员熟知的材料，例如集流体的材料可以包括但不限于：铜、镍、钛、钼、铝、铁、锌、或不锈钢中的至少一种，或者使用导电无机材料，例如，碳或石墨烯。这些材料可以单独使用一种，也可以两种以上组合使用。
以下，举出实施例及比较例来对本申请的实施方式进行更具体地说明，但本申请并不限于这些实施例。
实施例1
1、将100g硅氧材料分散于500mL的含水正己烷中，搅拌均匀，其中硅氧材料为SiO(一氧化硅)，正己烷含水量为5Vol％；
2、将0.5g TPS(三乙氧基乙烯基硅烷)溶于步骤1得到的混合液中；
3、将催化剂按照SiO添加量的1/10加入到步骤2得到的混合液中，升温至60℃搅拌2小时后，去除溶剂并烘干后，得到前驱体，其中催化剂为浓度2.5mol/L的草酸溶液；
4、将步骤3得到前驱体在氩气气体中烧结，烧结温度为600℃，保温2h，升温速率为3℃/min，得到负极材料。
实施例2
除了烧结温度为800℃以外，其余与实施例1相同。
实施例3
除了烧结温度为1000℃以外，其余与实施例1相同。
实施例4
除了硅氧烷原料选用TVS(三乙氧基乙烯基硅烷)以外，其余与实施例1相同。
实施例5
除了硅氧烷原料选用DPS(二乙氧基二苯基硅烷)以外，其余与实施例1相同。
实施例6
除了硅氧烷原料选用BSB(1，4-双(三乙氧基甲硅烷基)苯)以外，其余与实施例1相同。
实施例7
除了硅氧烷原料选用PDMS(二甲基硅氧烷)，PDMS添加量为2g以外，其余与实施例1相同。
实施例8
除了PDMS添加量为1g以外，其余与实施例7相同。
实施例9
除了PDMS添加量为0.5g以外，其余与实施例7相同。
实施例10
除了硅氧材料为含锂硅氧材料以外，其余与实施例6相同，锂占上述含锂硅氧材料质量的8％。
实施例11
除了硅氧材料为含镁硅氧材料以外，其余与实施例6相同，镁占上述含镁硅氧材料质量的13％。
对比例1
1、将100g硅氧材料分散于500mL的含水正己烷中，搅拌均匀，其中硅氧材料为SiO(一氧化硅)，正己烷含水量为5Vol％；
2、将步骤1所得混合液去除溶剂并烘干后，在惰性气体中烧结，烧结温度为600℃，保温2h，升温速率为3℃/min，得到负极材料。
对比例2
除了硅氧材料为含锂硅氧材料以外，其余与对比例1相同，锂占上述含锂硅氧材料质量的8％。
对比例3
除了硅氧材料为含镁硅氧材料以外，其余与对比例1相同，镁占上述含镁硅氧材料质量的13％。
其中，上述各实施例及对比例中，SiO的制备过程为：将二氧化硅与金属硅粉末以摩尔比1:5至5:1混合，得到混合材料；在10 -4至10 -1kPa条件下，在1200至1450℃的温度范围内加热混合材料0.5至24h获得气体；冷凝获得的气体，得到固体，然后粉碎和筛分所得固体，得到SiO。
含锂硅氧材料可以为SiO的预嵌锂材料，锂占含锂硅氧材料质量的6％至12％；含镁硅氧材料可以为SiO的预嵌镁材料，镁占含镁硅氧材料质量的5％至20％。
<性能测试>
负极材料粉末性质测试：
粉末颗粒微观形貌观察：利用扫面电镜对负极材料进行粉末微观形貌观 察表征材料表面包覆情况，所选测试仪器为：OXFORD EDS(X-max-20mm2)，加速电压为10KV调整焦距，观测倍数从50K进行高倍观察，低倍下500-2000主要观察颗粒团聚情况。
负极材料比表面积测试：
在恒温低温下，测定不同相对压力时的气体在固体表面的吸附量后，基于布朗诺尔-埃特-泰勒吸附理论及其公式(BET公式)求得试样单分子层吸附量，从而计算出固体的比表面积。
测试时，称取1.5至3.5g粉末样品装入比表面积和孔隙度分析仪(型号TriStar II 3020)的测试测试样品管中，200℃脱气120min后进行测试。
负极材料粒度测试：
50ml洁净烧杯中加入0.02g粉末样品，加入20ml去离子水，再滴加几滴1％的表面活性剂，使粉末完全分散于水中，然后于功率120W超声清洗机中超声震荡5分钟，利用激光粒度分析仪(型号MasterSizer 2000)测试粒度分布。
负极材料振实密度测试：采用GB/T 5162-2006《金属粉末振实密度的测定》。
负极材料碳含量测试：
负极材料样品在富氧条件下由高频炉高温加热燃烧，使碳、硫氧化成二氧化碳、二氧化硫，该气体经处理后进入相应的吸收池，对相应的红外辐射进行吸收再由探测器转化成对应的信号。此信号由计算机采样，经线性校正后转换成与二氧化碳、二氧化硫浓度成正比的数值，然后把整个分析过程的取值累加，分析结束后，此累加值在计算机中除以重量值，再乘以校正系数，扣除空白，即可获得样品中碳、硫百分含量。利用高频红外碳硫分析仪(型号为上海徳凯HCS-140)进行样品测试。
负极材料表面原子比测试：
在含有负极材料洒在导电胶的铜箔上，剪成的断面采用等离子抛光机(Leica EM TIC 3X‐Ion Beam Slope Cutter)抛光，随后放入扫描电子显微镜(SEM)中寻找到切开的硅基颗粒，采用聚焦离子束(FIB)将上述硅基颗粒沿断面的垂直方向切割，得到含有硅基颗粒截面的薄片(约50nm)后，采用 TEM测量，取距离外表面1至2nm的点进行能谱仪(EDS)测试，得到Si:O:C之比。
图1为实施例6制得的负极材料的截面FIB-TEM结构图，从图中能够看到明显的SiOC层结构，SiOC层厚度约4nm。
图2为对比例1制得的负极材料的截面FIB-TEM结构图，从图中无法看到SiOC层结构。
负极材料I2/I1测试：
XRD测试：称取负极材料样品1.0-2.0g倒入玻璃样品架的凹槽内，并用玻璃片将其压实和磨平，采用X射线衍射仪(型号布鲁克，D8)按照JJS K 0131-1996《X射线衍射分析法通则》进行测试，测试电压设置40kV，电流为30mA，扫描角度范围为10-85°，扫描步长为0.0167°，每个步长所设置的时间为0.24s，得到XRD衍射图，从图中得到2θ归属于28.4°的最高强度数值I1，与归属于21.0°的最高强度I2，从而计算出I2/I1的比值。
半电池首次效率测试：
将各实施例及对比例制备的负极材料与导电炭黑、聚合物按照80：10：10的比例混合，加去离子水后经过搅形成浆料，利用刮刀在集流体表面涂覆100μm厚度的涂层，85℃条件下经过12小时真空干燥箱烘干后，利用冲压机在干燥环境中切成直径为1cm的圆片，在手套箱中以金属锂片作为对电极，隔离膜选择ceglard复合膜，加入电解液组装成扣式电池，运用蓝电(LAND)系列电池测试测试对电池进行充放电测试，首次效率计算方式为，放电截至电压为2.0V的容量/充电电压截至到0.005V对应的容量，测试结果如表1所示。
半电池克容量计算方式：
半电池放电截至电压为2.0V对应的克容量。
全电池性能测试：
循环性能测试：
测试温度为25℃或45℃，以0.7C恒流充电到4.4V，恒压充电到0.025C，静置5分钟后以0.5C放电到3.0V。以此步骤得到的容量为初始容量，进行0.7C充电/0.5C放电进行循环测试，以每一步的容量与初始容量做比值，得到容量 衰减曲线。以25℃循环截至容量保持率为90％的圈数记为电池的室温循环性能，以45℃循环截至容量保持率为80％的圈数记为电池的高温循环性能，通过比较上述两种情况下的循环圈数比较材料的循环性能。各实施例和对比例循环性能如表2所示。
放电倍率测试：
在25℃下，以0.2C放电到3.0V，静置5min，以0.5C充电到4.45V，恒压充电到0.05C后静置5分钟，调整放电倍率，分别以0.2C、0.5C、1C、1.5C、2.0C进行放电测试，分别得到放电容量，以每个倍率下2C放电容量与0.2C放电容量比值为倍率性能。
锂离子电池满充膨胀率测试：
用螺旋千分尺测试锂离子电池半充，即50％充电状态(SOC)时新鲜电池的厚度，循环至400圈时，电池处于满充，即100％SOC状态下，再用螺旋千分尺测试此时电池的厚度，与初始半充时新鲜电池的厚度对比，即可得此时满充锂离子电池的膨胀率。
全电池制备：
锂离子电池的制备：
正极的制备：
将LiCoO 2、导电炭黑和聚偏二氟乙烯(PVDF)按照95％:2.5％:2.5％的重量比在N-甲基吡咯烷酮溶剂体系中充分搅拌混合均匀，制得固含量为75wt％的正极浆料。将制得的正极浆料涂布在正极集流体铝箔上，烘干，冷压，得到涂层厚度为110μm的正极。
负极的制备：
将石墨、根据实施例和对比例制备的负极材料、导电剂和粘结剂按照70％:15％:5％:10％的重量比混合，加入适量的水，在固体含量为55wt％至70wt％下捏合，再加入适量的水，调节浆料的粘度为4000至6000Pa·s，制成负极浆料，将制得的负极浆料涂布在负极集流体铜箔上，经烘干，冷压，得到涂层厚度为100μm的负极。其中，导电剂选用导电碳黑，粘结剂选用聚丙烯酸(PAA)。
电解液的制备：
在干燥氩气环境下，在碳酸丙烯酯(PC)，碳酸乙烯酯(EC)，碳酸二乙酯(DEC)混合而成的溶剂中，加入LiPF 6并混合均匀，再加入12.5wt％的氟代碳酸乙烯酯(FEC)，混合均匀得到电解液。其中，碳酸丙烯酯，碳酸乙烯酯，碳酸二乙酯的重量比为1：1：1，LiPF 6的浓度为1.15mol/L。
隔离膜的制备：
以厚度为15μm的聚乙烯(PE)多孔聚合薄膜作为隔离膜。
锂离子电池的制备：
将正极、隔离膜、负极按顺序叠好，使隔离膜处于正极和负极中间以起到隔离的作用，卷绕得到电极组件，将电极组件置于外包装中，注入电解液，封装，经过化成、脱气、切边等工艺流程得到锂离子电池。
表1各实施例、对比例中负极材料的参数及半电池测试结果
Figure PCTCN2020086434-appb-000001
Figure PCTCN2020086434-appb-000002
表2使用各实施例、对比例的负极材料制得的锂离子电池性能测试结果
Figure PCTCN2020086434-appb-000003
Figure PCTCN2020086434-appb-000004
实施例1至6、8至9与对比例1对比说明，表面存在SiOC的负极材料相比于表面不存在SiOC的负极材料，锂离子电池在不同温度下的循环性能明显改善，膨胀率和放电倍率性能也得到改善。并且从实施例1至3可以看出，随着烧结温度逐渐升高，负极材料表面的碳元素逐渐降低，循环性能逐渐降低，膨胀率和放电倍率逐渐增加，因此选择较低的温度效果较好，优选600℃。
实施例7与对比例1对比后可知，25℃循环圈数稍大于对比例1，45℃循环圈数稍小于对比例1，但膨胀率和放电倍率均明显得到改善，这可能是由于PDMS加入量较多，因PDMS自身在负极材料表面平铺性能较差，因此更多的PDMS加入量反而更容易造成表面的不稳定，对锂离子电池的循环性能带来影响，但对锂离子电池的膨胀率和放电倍率均能改善。
实施例10与对比例2对比说明，在同样为含Li元素硅氧烷材料的情况下， 表面存在SiOC的负极材料相比于表面不存在SiOC的负极材料，锂离子电池在不同温度下的循环性能明显改善，膨胀率和放电倍率性能也得到改善。
实施例11与对比例3对比说明，在同样为含Mg元素硅氧烷材料的情况下，表面存在SiOC的负极材料相比于表面不存在SiOC的负极材料，锂离子电池在不同温度下的循环性能明显改善，膨胀率和放电倍率性能也得到改善。
实施例7至9与对比例1对比说明，添加不同含量硅氧烷材料制备表面存在SiOC的负极材料，相比于表面不存在SiOC的负极材料，锂离子电池的循环性能明显改善，膨胀率和放电倍率性能也得到改善。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，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，均应包含在本申请保护的范围之内。

Claims (14)

  1. 一种负极材料，包括硅基颗粒及存在于该硅基颗粒表面的SiOC，其中，
    所述SiOC中Si、O、C的原子比为1：0.5至5：0.5至10；
    所述负极材料的Dv50为2.5μm至10μm，所述SiOC占负极材料质量的0.1％至20％。
  2. 根据权利要求1所述的负极材料，其中，所述SiOC为无定形结构。
  3. 根据权利要求1所述的负极材料，其中，所述硅基颗粒的粒径分布满足：0.3≤Dn10/Dv50≤0.6。
  4. 根据权利要求1所述的负极材料，其中，所述硅基颗粒包括纳米硅颗粒、氧化亚硅颗粒或碳硅复合颗粒中的至少一种。
  5. 根据权利要求1所述的负极材料，其中，所述硅基颗粒中包括Li元素或Mg元素中的至少一种。
  6. 根据权利要求1所述的负极材料，所述SiOC是由硅氧烷原料经热解反应而形成的，所述硅氧烷原料包括硅氧烷、硅氧烷水解产物或硅烷树脂中的至少一种。
  7. 根据权利要求6所述的负极材料，所述硅氧烷包括甲基三乙氧基硅烷，乙基三乙氧基硅烷，乙烯基三乙氧基硅烷，苯基三乙氧基硅烷，二苯基三乙氧基硅烷，二乙氧基甲基苯基硅烷，甲基三甲氧基硅烷，苄基三乙氧基硅烷，乙烯基三甲氧基硅烷，异丁基三乙氧基硅烷，二甲氧基(甲基)苯基硅烷，环己基甲基二甲氧基硅烷，辛基三甲氧基硅烷，丙基三甲氧基硅烷，十八烷基三乙氧基硅烷，己基三乙氧基硅烷，辛基甲基二甲氧基硅烷，二甲基二乙氧基硅烷，十八烷基三甲氧基硅烷，十二烷基三乙氧基硅烷，烯丙基三甲氧基硅烷，十六烷基三甲氧基硅烷，甲基乙烯基二乙氧基硅烷，正辛基三乙氧基硅烷，二异丁基二甲氧基硅烷，(氯甲基)二乙氧基(甲基)硅烷，二甲氧基甲基乙烯基硅烷，γ-氨丙基甲基二乙氧基硅烷或1,4-双(三乙氧基甲硅烷基)苯中的至少一种；
    所述硅烷树脂包含有机硅树脂，所述有机硅树脂包括脂肪族基团硅烷树脂或苯基硅烷树脂中的至少一种。
  8. 根据权利要求1所述的负极材料，其中，所述硅基颗粒的表面还存在 化学式MeO y代表的氧化物，Me元素包括Al、Si、Ti、Mn、V、Cr、Co或Zr中的至少一种，0.5≤y≤3，所述氧化物中包含碳材料。
  9. 根据权利要求1所述的负极材料，其中，所述硅基颗粒的表面还存在聚合物，所述聚合物中包含碳材料。
  10. 根据权利要求9所述的负极材料，其中，所述聚合物包括聚偏氟乙烯、羧甲基纤维素、羧甲基纤维素钠、聚乙烯基吡咯烷酮、聚丙烯酸、聚丁苯橡胶、聚丙烯酰胺、聚酰亚胺、聚酰胺酰亚胺或上述物质衍生物中的至少一种。
  11. 根据权利要求8或9所述的负极材料，所述碳材料包括碳纳米管、碳纳米颗粒、碳纤维或石墨烯中的至少一种。
  12. 一种负极极片，包括权利要求1-11中任一项所述的负极材料。
  13. 一种电化学装置，包括：正极极片；
    负极极片；
    隔膜，所述隔膜位于所述正极极片和所述负极极片之间；以及
    电解液；
    其中，所述负极极片为权利要求12所述的负极极片。
  14. 一种电子装置，包括权利要求13所述的电化学装置。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122376A (zh) * 2021-11-12 2022-03-01 宁德新能源科技有限公司 一种电化学装置及包含其的电子装置
WO2023202636A1 (zh) * 2022-04-21 2023-10-26 贝特瑞新材料集团股份有限公司 负极材料及其制备方法和锂离子电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115810731B (zh) * 2022-11-22 2024-09-17 中国人民解放军国防科技大学 硅基负极材料及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102299338A (zh) * 2011-07-27 2011-12-28 中国人民解放军国防科学技术大学 用于制备锂离子电池负极的SiOC陶瓷材料及其制备方法和锂离子电池
KR20160045378A (ko) * 2014-10-17 2016-04-27 주식회사 케이씨씨 실리콘-실리콘 옥시카바이드 복합체, 이의 제조 방법, 이를 포함하는 음극 활물질 및 리튬이차전지
KR20170141020A (ko) * 2016-06-14 2017-12-22 한국과학기술연구원 실리콘옥시카바이드 복합체, 이의 제조방법 및 이를 포함하는 나트륨 이차전지용 음극소재
CN107658452A (zh) * 2017-09-19 2018-02-02 合肥国轩高科动力能源有限公司 一种硅/碳纳米管/碳氧化硅复合材料及制备方法和应用
EP3597597A1 (en) * 2018-07-17 2020-01-22 Commissariat à l'Energie Atomique et aux Energies Alternatives Spherical sioc particulate electrode material
CN110797520A (zh) * 2019-11-14 2020-02-14 宁德新能源科技有限公司 负极材料及包含其的电化学装置和电子装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004273377A (ja) * 2003-03-12 2004-09-30 Mitsubishi Materials Corp 充放電可能な無機化合物及びその製造方法並びにこれを用いた非水電解液二次電池
JP2004335334A (ja) * 2003-05-09 2004-11-25 Mitsubishi Materials Corp 非水電解液二次電池用負極材料及びその製造方法並びにこれを用いた非水電解液二次電池
EP3018099A1 (en) * 2014-11-06 2016-05-11 Commissariat A L'energie Atomique Et Aux Energies Alternatives SiOC composite electrode material
JP6547309B2 (ja) * 2015-01-29 2019-07-24 東レ株式会社 リチウムイオン二次電池用負極材料、リチウムイオン二次電池負極用ペースト、リチウムイオン二次電池用負極およびリチウムイオン二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102299338A (zh) * 2011-07-27 2011-12-28 中国人民解放军国防科学技术大学 用于制备锂离子电池负极的SiOC陶瓷材料及其制备方法和锂离子电池
KR20160045378A (ko) * 2014-10-17 2016-04-27 주식회사 케이씨씨 실리콘-실리콘 옥시카바이드 복합체, 이의 제조 방법, 이를 포함하는 음극 활물질 및 리튬이차전지
KR20170141020A (ko) * 2016-06-14 2017-12-22 한국과학기술연구원 실리콘옥시카바이드 복합체, 이의 제조방법 및 이를 포함하는 나트륨 이차전지용 음극소재
CN107658452A (zh) * 2017-09-19 2018-02-02 合肥国轩高科动力能源有限公司 一种硅/碳纳米管/碳氧化硅复合材料及制备方法和应用
EP3597597A1 (en) * 2018-07-17 2020-01-22 Commissariat à l'Energie Atomique et aux Energies Alternatives Spherical sioc particulate electrode material
CN110797520A (zh) * 2019-11-14 2020-02-14 宁德新能源科技有限公司 负极材料及包含其的电化学装置和电子装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122376A (zh) * 2021-11-12 2022-03-01 宁德新能源科技有限公司 一种电化学装置及包含其的电子装置
CN114122376B (zh) * 2021-11-12 2024-05-14 宁德新能源科技有限公司 一种电化学装置及包含其的电子装置
WO2023202636A1 (zh) * 2022-04-21 2023-10-26 贝特瑞新材料集团股份有限公司 负极材料及其制备方法和锂离子电池

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