WO2015014121A1 - 锂离子二次电池负极活性材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池 - Google Patents

锂离子二次电池负极活性材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池 Download PDF

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WO2015014121A1
WO2015014121A1 PCT/CN2014/072477 CN2014072477W WO2015014121A1 WO 2015014121 A1 WO2015014121 A1 WO 2015014121A1 CN 2014072477 W CN2014072477 W CN 2014072477W WO 2015014121 A1 WO2015014121 A1 WO 2015014121A1
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nitrogen
active material
silicon
secondary battery
ion secondary
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French (fr)
Chinese (zh)
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夏圣安
杨俊�
王平华
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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Priority to ES14806158T priority Critical patent/ES2733374T3/es
Priority to EP14806158.3A priority patent/EP2876710B1/en
Priority to JP2016514251A priority patent/JP6169260B2/ja
Priority to KR1020157032657A priority patent/KR20150143767A/ko
Priority to US14/580,030 priority patent/US10454094B2/en
Publication of WO2015014121A1 publication Critical patent/WO2015014121A1/zh
Anticipated expiration legal-status Critical
Priority to US16/586,268 priority patent/US20200028150A1/en
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—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
    • H01M4/364—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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 invention relates to the field of lithium ion secondary batteries, and more particularly to a lithium ion secondary battery negative active material and a method for preparing the same, a lithium ion secondary battery negative electrode sheet and a lithium ion secondary battery. Background technique
  • the first aspect of the embodiments of the present invention provides a novel lithium ion secondary battery anode active material, which solves the problem that the volume change of the silicon material as the anode active material in the prior art is easy to fall off from the current collector and conductance. The problem of low rates.
  • an embodiment of the present invention provides a negative active material for a lithium ion secondary battery, comprising a silicon-based active material and a nitrogen-doped carbon material, wherein the silicon-based active material is encapsulated in the nitrogen-doped carbon material
  • the silicon-based active material is one or more of a nanoparticle and a nanowire
  • the particle diameter of the silicon-based active material nanoparticle is 1 ⁇ 1 ⁇ ⁇
  • the diameter of the nanowire is l ⁇ 200nm and having a length of 1 ⁇ 10 ⁇ m
  • the nitrogen-doped carbon material has micropores in at least one of the surface and the inner portion, and the micropore pore size is distributed between 0.5 and 500 nm
  • the nitrogen-doped carbon material is a nitrogen-doped carbon network, and the nitrogen atom and the carbon atom in the nitrogen-doped carbon network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen, and a
  • the silicon-based active material accounts for 0.1% to 80% by mass of the lithium ion secondary battery negative electrode active material.
  • the ratio of the particle diameter of the silicon-based active material nanoparticles to the pore diameter of the pores is from 1 to 10:1.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material comprises a plurality of mutually cross-linked branches, the branches having a diameter of 1 ⁇ 10 ⁇ .
  • the nitrogen-doped carbon network contains pyrrole-type nitrogen.
  • the pyrrole-type nitrogen in the nitrogen-doped carbon network can be combined with Li + to form a bond, which has good lithium storage performance.
  • the material of the silicon-based active material is selected from one or more of elemental silicon, silicon oxide and silicon alloy.
  • the first aspect of the present invention provides a lithium ion secondary battery anode active material, wherein the silicon-based active material is encapsulated in a nitrogen-doped carbon material, and the silicon-based active material is doped by nitrogen.
  • the carbon material is combined with the current collector, and at least one of the surface and the inside of the nitrogen-doped carbon material has micropores, and the micropores of the nitrogen-doped carbon material can reserve space for expansion of the silicon-based active material, and the expanded silicon base
  • the binding of the active material to the nitrogen-doped carbon material does not fall off, which solves the problem that the volume change of the silicon material as the negative electrode active material in the prior art is easy to fall off from the current collector and the conductivity is low, and the lithium ion II is greatly extended.
  • the service life of the secondary battery anode active material, while the nitrogen-doped carbon network can increase the overall conductivity of the silicon-based active material/nitrogen-doped carbon material composite material, and the nitrogen-doped carbon network itself has a certain capacity plus a silicon base.
  • the high capacity of the active material itself makes the lithium ion secondary battery negative active material have a high capacity advantage.
  • lithium ion secondary batteries have lower cost of negative active materials and are easy to industrialize.
  • an embodiment of the present invention provides a method for preparing a negative active material for a lithium ion secondary battery. Preparation method, prepared according to one of the following methods:
  • Method 1 dispersing a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m in a solution to prepare a mixed solution, adding an oxidizing agent to the mixed solution, and then adding an organic molecular monomer, the organic molecular single
  • the body is selected from one or more of a pyridine monomer, a pyrrole monomer, an aniline monomer and a derivative thereof, and the silicon-based active material reacts with the organic molecular monomer to form a black precipitate, which is filtered and taken as a filter residue, followed by Forming a nitrogen-doped carbon material on the surface of the silicon-based active material by a pyrolysis method to obtain a lithium ion secondary battery anode active material;
  • Method 2 placing a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m in a tube furnace, and carrying a gasified organic molecular monomer with a protective gas, the organic molecular monomer being selected from the group consisting of pyridine monomers, One or more of a pyrrole monomer, an aniline monomer and a derivative thereof, and a nitrogen-doped carbon material is coated on the surface of the silicon-based active material by a chemical vapor deposition method to obtain a lithium ion secondary battery anode active material ;
  • Method 3 One or more organic molecules of the ionic liquid 3-mercapto-butylpyridine dicyanamide or 1-ethyl-3-mercaptoimidazolium diamine and its derivatives and the particle size of 1 ⁇ a mixed solution of ⁇ 1 ⁇ ⁇ of silicon-based active material is prepared, and then a nitrogen-doped carbon material is coated on the surface of the silicon-based active material by an ionic liquid pyrolysis method to obtain a lithium ion secondary battery anode active material;
  • the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material is encapsulated inside the nitrogen-doped carbon material, and the silicon-based active material is a nanoparticle And one or more of the nanowires, the silicon-based active material nanoparticles have a particle diameter of 1 ⁇ 1 ⁇ ⁇ , the nanowires have a diameter of 1 to 200 nm and a length of 1 to 10 ⁇ ⁇ , At least one of the surface and the inside of the nitrogen-doped carbon material has micropores, the micropore pore size is distributed between 0.5 and 500 nm, and the nitrogen-doped carbon material is made of a nitrogen-doped carbon mesh, the nitrogen doping
  • the nitrogen atom and the carbon atom in the carbon network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • the nitrogen-doped carbon material on the surface of the silicon-based active material by pyrolysis is as follows: the filter residue is dried at 60 to 100 ° C for 12 to 36 hours, and the dried residue is filtered. It is placed in a tube furnace, passed through a protective gas, and sintered at 500 to 1300 ° C for 1 to 6 hours.
  • the carbon-doped carbon material on the surface of the silicon-based active material by chemical vapor deposition is as follows: the mass ratio of the silicon-based active material to the organic molecular monomer is 1:1 ⁇ 10, the protective gas flow rate is controlled to 10 ⁇ 100 ml/min, and the temperature in the tube furnace is raised to 500 ⁇ 1300 °C at a heating rate of 10 ⁇ 50 °C/min and kept for 1 ⁇ 12h, then cooled to room temperature. .
  • the nitrogen-doped carbon material coated on the surface of the silicon-based active material by the ionic liquid pyrolysis method is as follows: the mixed solution is placed in a tube furnace, and the tube furnace is evacuated. Passing protective gas, the flow rate of protective gas is controlled to 10 ⁇ 100 ml/min, and the temperature in the tube furnace is raised to 500 ⁇ 1300 °C at a heating rate of 1 ⁇ 10 °C /min and kept for l ⁇ 6h, then Cool to room temperature.
  • the method for preparing a negative active material for a lithium ion secondary battery provided by the second aspect of the present invention is simple, convenient, low in cost, and easy to industrialize.
  • an embodiment of the present invention provides a negative electrode tab for a lithium ion secondary battery, the negative electrode tab of the lithium ion secondary battery including a current collector and a lithium ion secondary battery negative electrode coated on the current collector
  • An active material, the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material being encapsulated inside the nitrogen-doped carbon material, the silicon-based active material
  • the nano-particles and the nanowires have a particle diameter of 1 ⁇ 1 ⁇ ⁇ , and the nanowires have a diameter of 1 to 200 nm and a length of 1 to 10 ⁇ ⁇ .
  • a lithium ion secondary battery negative electrode tab provided by the third aspect of the present invention has a long service life and good electrical conductivity.
  • an embodiment of the present invention provides a lithium ion secondary battery, which is composed of a lithium ion secondary battery negative electrode pole piece, a positive electrode pole piece, a separator, a non-aqueous electrolyte, and an outer casing.
  • the lithium ion secondary battery negative electrode tab includes a current collector and is coated on the current collector a lithium ion secondary battery anode active material, the lithium ion secondary battery anode active material comprising a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material being encapsulated inside the nitrogen-doped carbon material
  • the silicon-based active material is one or more of a nanoparticle and a nanowire, the silicon-based active material nanoparticle has a particle diameter of 1 nm to 1 ⁇ m, and the nanowire has a diameter of 1 to 200 nm and a length.
  • the nitrogen atom and the carbon atom in the nitrogen-doped carbon network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • the binding of the doped carbon material does not fall off, which solves the problem that the volume change of the silicon material as the negative electrode active material in the prior art is easy to fall off from the current collector and the conductivity is low, and the negative electrode activity of the lithium ion secondary battery is greatly prolonged.
  • the service life of the material while the nitrogen-doped carbon network can increase the overall conductivity of the silicon-based active material/nitrogen-doped carbon material composite, and the nitrogen-doped carbon network itself has a certain capacity plus the silicon-based active material itself.
  • the high capacity makes the lithium ion secondary battery anode active material have a high capacity advantage.
  • the lithium ion secondary battery anode active material has a low cost and is easy to industrially produce.
  • the method for preparing a lithium ion secondary battery anode active material provided by the second aspect of the present invention is simple, convenient, low in cost, and easy to industrialize.
  • a lithium ion secondary battery negative electrode tab provided in a third aspect of the invention and a lithium ion secondary battery provided in the fourth aspect have a long service life and a good electrical conductivity.
  • Fig. 1 is a TEM electron micrograph of a negative active material for a lithium ion secondary battery produced in Example 1 of the present invention.
  • Example 2 is a schematic view showing the structure of a nitrogen-doped carbon network in a negative active material of a lithium ion secondary battery produced in Example 2 of the present invention. detailed description
  • the first aspect of the present invention provides a novel lithium ion secondary battery anode active material, which solves the problem that the volume change of the silicon material as the anode active material is easy to fall off from the current collector and the conductivity is low in the prior art.
  • the second aspect of the embodiments of the present invention provides a method for preparing the lithium ion secondary battery anode active material, which is simple and convenient in process, low in cost, and easy to industrialize.
  • a third aspect of the present invention provides a lithium ion secondary battery negative electrode sheet comprising the lithium ion secondary battery negative electrode active material, and a fourth aspect of the present invention provides the lithium ion secondary battery negative electrode activity. Materials for lithium ion secondary batteries.
  • an embodiment of the present invention provides a negative active material for a lithium ion secondary battery, comprising a silicon-based active material and a nitrogen-doped carbon material, wherein the silicon-based active material is encapsulated in the nitrogen-doped carbon material Internally, the silicon-based active material is one or more of a nanoparticle and a nanowire, the silicon-based active material nanoparticle has a particle diameter of 1 ⁇ 1 ⁇ ⁇ , and the nanowire has a diameter of 1 to 200 nm.
  • the silicon-based active material accounts for 0.1% to 80% by mass of the lithium ion secondary battery negative electrode active material. More preferably, the silicon-based active material accounts for 5% to 50% by mass of the lithium ion secondary battery negative electrode active material. Further preferably, the silicon-based active material accounts for 15% to 30% by mass of the lithium ion secondary battery negative electrode active material.
  • the silicon-based active material nanoparticles have a particle diameter of from 1 to 200 nm.
  • the nanowire of the silicon-based active material has a diameter of 1 to 50 nm and a length of 1 to 5 ⁇ m.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material comprises a plurality of mutually cross-linked branches, the branches having a diameter of 1 ⁇ 10 ⁇ .
  • the pore diameter of the micropores is distributed between 2 and 100 nm.
  • the ratio of the particle diameter of the silicon-based active material nanoparticles to the pore diameter of the pores is from 1 to 10:1.
  • the nitrogen-doped carbon material has a microporous structure on the surface or inside, or has a microporous structure on the surface and inside of the nitrogen-doped carbon material.
  • the nitrogen-doped carbon network contains pyrrole-type nitrogen.
  • the pyrrole-type nitrogen in the nitrogen-doped carbon network can be combined with Li + to form a bond, which has good lithium storage performance.
  • the material of the silicon-based active material is selected from one or more of elemental silicon, silicon oxide and silicon alloy.
  • the first aspect of the present invention provides a lithium ion secondary battery anode active material, wherein the silicon-based active material is encapsulated in a nitrogen-doped carbon material, and the silicon-based active material is doped by nitrogen.
  • the carbon material is combined with the current collector, and at least one of the surface and the inside of the nitrogen-doped carbon material has micropores, and the micropores of the nitrogen-doped carbon material can reserve space for expansion of the silicon-based active material, and the expanded silicon base
  • the binding of the active material to the nitrogen-doped carbon material does not fall off, which solves the problem that the volume change of the silicon material as the negative electrode active material in the prior art is easy to fall off from the current collector and the conductivity is low, and the lithium ion II is greatly extended.
  • the service life of the negative electrode active material of the secondary battery, and the nitrogen-doped carbon mesh can improve the overall conductivity of the silicon-based active material/nitrogen-doped carbon material composite material,
  • the nitrogen-doped carbon network itself has a certain capacity plus the high capacity of the silicon-based active material itself, so that the lithium ion secondary battery anode active material has a high capacity advantage.
  • lithium ion secondary batteries have lower anode active materials and are easier to industrially produce.
  • an embodiment of the present invention provides a method for preparing a negative active material for a lithium ion secondary battery, which is prepared according to one of the following methods:
  • Method 1 dispersing a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m in a solution to prepare a mixed solution, adding an oxidizing agent to the mixed solution, and then adding an organic molecular monomer, the organic molecular single
  • the body is selected from one or more of a pyridine monomer, a pyrrole monomer, an aniline monomer and a derivative thereof, and the silicon-based active material reacts with the organic molecular monomer to form a black precipitate, which is filtered and taken as a filter residue, followed by Forming a nitrogen-doped carbon material on the surface of the silicon-based active material by a pyrolysis method to obtain a lithium ion secondary battery anode active material;
  • Method 2 placing a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m in a tube furnace, and carrying a gasified organic molecular monomer with a protective gas, the organic molecular monomer being selected from the group consisting of pyridine monomers, One or more of a pyrrole monomer, an aniline monomer and a derivative thereof, and a nitrogen-doped carbon material is coated on the surface of the silicon-based active material by a chemical vapor deposition method to obtain a lithium ion secondary battery anode active material ;
  • the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material is encapsulated inside the nitrogen-doped carbon material, and the silicon-based active material is a nanoparticle And one or more of the nanowires, the silicon-based active material nanoparticles have a particle diameter of 1 ⁇ 1 ⁇ ⁇ , the nanowires have a diameter of 1 to 200 nm and a length of 1 to 10 ⁇ ⁇ , At least one of the surface and the interior of the nitrogen-doped carbon material has micropores, and the pore size of the pores is distributed
  • the material of the nitrogen-doped carbon material is a nitrogen-doped carbon network, and the nitrogen-doped carbon network
  • the nitrogen atom and the carbon atom are combined in a form of at least one of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • the nitrogen-doped carbon material on the surface of the silicon-based active material by pyrolysis is as follows: the filter residue is dried at 60 to 100 ° C for 12 to 36 hours, and the dried residue is filtered. It is placed in a tube furnace, passed through a protective gas, and sintered at 500 to 1300 ° C for 1 to 6 hours.
  • an organic molecular monomer selected from the group consisting of a pyridine monomer, a pyrrole monomer, and an aniline.
  • the thermal reaction of C is carried out for 12 ⁇ 36 h to form a black precipitate, which is filtered, washed with filter residue, and then the filter residue is dried at 60 ⁇ 100 ° C for 12 to 36 hours.
  • the dried filter residue is placed in a tube furnace and passed into a protective furnace.
  • the gas was sintered at 500 to
  • a solution of cetyltrimethylammonium bromide (CTAB) is disposed in an ice water bath with 0.5 to 2 mol/L of hydrochloric acid, and a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m is further added.
  • CTL cetyltrimethylammonium bromide
  • the carbon-doped carbon material coated on the surface of the silicon-based active material by chemical vapor deposition is as follows: the mass ratio of the silicon-based active material to the organic molecular monomer is 1:1 ⁇ 10, the protective gas flow rate is controlled to 10 ⁇ 100 ml/min, and the temperature in the tube furnace is raised to 500 ⁇ 1300 °C at a heating rate of 10 ⁇ 50 °C/min and kept for 1 ⁇ 12h, then cooled to room temperature. .
  • the silicon-based active material having a particle diameter of 1 ⁇ to 1 ⁇ is placed in a tube furnace, and the tube furnace is evacuated, and the vaporized organic molecular monomer is brought into the protective gas, and the organic molecular monomer is selected from the group consisting of One or more of a pyridine monomer, a pyrrole monomer, an aniline monomer, and a derivative thereof, the silicon-based active material and the
  • the mass ratio of the organic molecular monomer is 1:1 to 10, and the flow rate of the protective gas is controlled to be 10 to 100 ml/min, and the temperature in the tube furnace is raised to 500 to 1300 ° at a heating rate of 10 to 50 ° C / min. C was kept for 1 to 12 hours, and then cooled to room temperature to obtain a lithium ion secondary battery negative electrode active material.
  • the particle size is placed in a quartz tube lnm ⁇ l ⁇ ⁇ silicon-based active material, and then into a tube furnace, the tube furnace was evacuated to 0 ⁇ 10- 2 Pa, with a protective gas Bringing a vaporized pyridine monomer, the mass ratio of the silicon-based active material to the pyridine monomer is 1:1 to 10, and the shielding gas flow rate is controlled to 10 to 100 ml/min, to 10 to 50°.
  • the heating rate of C/min was raised to 500 to 1300 ° C in a tube furnace and kept for 1 to 12 hours, followed by cooling to room temperature to obtain a lithium ion secondary battery anode active material.
  • the nitrogen-doped carbon material on the surface of the silicon-based active material by the ionic liquid pyrolysis method is as follows: the mixed solution is placed in a tube furnace, and the tube furnace is evacuated. Passing protective gas, the flow rate of protective gas is controlled to 10 ⁇ 100 ml/min, and the temperature in the tube furnace is raised to 500 ⁇ 1300 °C at a heating rate of 1 ⁇ 10 °C /min and kept for l ⁇ 6h, then Cool to room temperature.
  • one or more of the ionic liquid 3-mercapto-butylpyridine dicyanamide salt or 1-ethyl-3-mercaptoimidazolium diamine and its derivatives are organic under a dry atmosphere
  • a silicon-based active material having a particle diameter of 1 nm to 1 ⁇ m for 30 to 120 minutes a mass ratio of the organic molecule to the silicon-based active material is 0.5 to 10:1, and then the mixture is moved to In the middle of the tube, put it into the tube furnace, vacuum the tube furnace to 0 ⁇ 10_ 2 Pa, and pass the protective gas.
  • the flow rate of the protective gas is 10 ⁇ 100 ml/min, l ⁇ 10 °C.
  • the heating rate of /min raises the temperature inside the tube furnace to
  • the anode active material of the lithium ion secondary battery was prepared by heating at 500 to 1300 ° C for 1 to 6 hours and then cooling to room temperature.
  • the organic molecular monomer is selected from one or more of a pyridine monomer, a pyrrole monomer, an aniline monomer and a derivative thereof, or is selected from the group consisting of an ionic liquid 3-mercapto-butylpyridine dicyanamide salt or 1-B.
  • a pyridine monomer a pyrrole monomer
  • aniline monomer an aniline monomer and a derivative thereof
  • benzyl-3-mercaptoimidazolium diamine and its derivatives One or more of benzyl-3-mercaptoimidazolium diamine and its derivatives.
  • the organic molecule acts as a carbon source to form a nitrogen-doped carbon network in a high temperature process, wherein the nitrogen atom and the carbon atom in the nitrogen-doped carbon network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen and a pyrrole type nitrogen.
  • the organic molecules decompose out a small molecule gas, and the small molecule gas escapes from the surface of the nitrogen-doped carbon material, thereby forming a microporous structure on the surface or inside of the nitrogen-doped carbon material, or in nitrogen doping
  • the surface and interior of the hybrid carbon material form a microporous structure.
  • the lithium ion secondary battery anode active material has a mass ratio of the silicon-based active material of from 0.1% to 80%. More preferably, the lithium ion secondary battery negative electrode active material has a mass ratio of the silicon-based active material of 5% to 50%. Further preferably, the mass ratio of the silicon-based active material in the negative electrode active material of the lithium ion secondary battery is 15% to 30%.
  • the pores of the micropores are distributed at 2 to 100 nm.
  • the ratio of the particle diameter of the silicon-based active material nanoparticles to the pore diameter of the pores is from 1 to 10:1.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material comprises a plurality of mutually cross-linked branches, the branches having a diameter of 1 ⁇ 10 ⁇ .
  • the nitrogen-doped carbon network contains pyrrole-type nitrogen.
  • the pyrrole-type nitrogen in the nitrogen-doped carbon network can be combined with Li + to form a bond, which has good lithium storage performance.
  • the material of the silicon-based active material is selected from one or more of elemental silicon, silicon oxide and silicon alloy.
  • the invention provides a lithium ion secondary battery anode active material provided by the second aspect of the present invention
  • the preparation method is simple and convenient, low in cost, and easy to industrialize.
  • an embodiment of the present invention provides a negative electrode tab for a lithium ion secondary battery, the negative electrode tab of the lithium ion secondary battery including a current collector and a lithium ion secondary battery negative electrode coated on the current collector
  • An active material, the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material being encapsulated inside the nitrogen-doped carbon material, the silicon-based active material
  • the nano-particles and the nanowires have a particle diameter of 1 ⁇ 1 ⁇ ⁇ , and the nanowires have a diameter of 1 to 200 nm and a length of 1 to 10 ⁇ ⁇ .
  • the nitrogen-doped carbon material having a pore size of 0.5 to 500 nm, and the material of the nitrogen-doped carbon material is a nitrogen-doped carbon network,
  • the nitrogen atom and the carbon atom in the nitrogen-doped carbon network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • a lithium ion secondary battery negative electrode tab provided by the third aspect of the present invention has a long service life and good electrical conductivity.
  • the preferred mode of the lithium ion secondary battery negative electrode active material is the same as the first aspect.
  • an embodiment of the present invention provides a lithium ion secondary battery, which is composed of a lithium ion secondary battery negative electrode pole piece, a positive electrode pole piece, a separator, a non-aqueous electrolyte, and an outer casing.
  • the negative electrode tab of the lithium ion secondary battery includes a silicon-based active material and a nitrogen-doped carbon material, the silicon-based active material is encapsulated inside the nitrogen-doped carbon material, and the silicon-based active material is a nanoparticle and One or more of the nanowires, the silicon-based active material nanoparticles have a particle diameter of 1 nm to 1 ⁇ m, and the nanowires have a diameter of 1 to 200 nm and a length of 1 to 10 ⁇ m, and the nitrogen At least one of the surface and the interior of the doped carbon material has micropores, the micropore pore size is distributed between 0.5 and 500 nm, and the nitrogen-doped carbon material is made of a nitrogen-doped carbon network, the nitrogen-doped carbon The nitrogen atom and the carbon atom in the network are combined in at least one of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • the lithium ion secondary battery provided by the fourth aspect of the embodiment of the present invention has a long service life and a good electrical conductivity.
  • the preferred mode of the lithium ion secondary battery negative electrode active material is the same as the first aspect.
  • a method for preparing a negative electrode active material for a lithium ion secondary battery comprising the steps of: dissolving cetyltrimethylammonium bromide (CTAB, (C 16 H 33 )N(CH 3 ) 3 Br, 7.3 g )
  • CAB cetyltrimethylammonium bromide
  • HC1 120 mL, 1 mol/L
  • APS ammonium persulfate
  • a white suspension was formed, and after stirring for 0.5 hour, a pyrrole monomer (Py, 12 mL) was added to the suspension at 4 .
  • the black precipitate was formed by incubation at 24 h, filtered, and the obtained filter residue was washed three times with 1 mol/L HCl solution, then washed with pure water until the solution was colorless neutral, and then the filter residue was dried at 80 ° C. After the hour, the dried filter residue was placed in a tube furnace, passed through a 5% H 2 /Ar mixture, and sintered at 700 ° C for 2 hours to obtain a lithium ion secondary battery negative electrode active material.
  • the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material, and the silicon-based active material is encapsulated inside the nitrogen-doped carbon material.
  • the silicon-based active material in the negative electrode active material of the lithium ion secondary battery is elemental silicon, and the mass ratio is 25.3% as measured by the ammonium chloride gravimetric method.
  • At least one of the surface and the inside of the nitrogen-doped carbon material has micropores, and the pore size distribution is 0.5 to 4 nm by nitrogen adsorption method, calculated by BET and BJH.
  • Fig. 1 is a TEM electron micrograph of a negative active material for a lithium ion secondary battery produced in Example 1 of the present invention.
  • the lithium ion secondary battery negative electrode active material includes a silicon-based active material and a nitrogen-doped carbon material.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material includes a plurality of cross-linked branches having a diameter of 50 to 80 nm.
  • the silicon-based active material is encapsulated inside the nitrogen-doped carbon material.
  • This structure makes full use of the three-dimensional conductive network of nitrogen-doped carbon materials, and the low conductivity of the silicon-based active material has little effect on the overall electrical conductivity of the material.
  • the micropores of the nitrogen-doped carbon material can effectively reduce the influence of the volume change of the silicon-based active material on the overall life of the material.
  • Embodiment 2 A method for preparing a negative active material for a lithium ion secondary battery, comprising the steps of: placing 3 g of silicon powder having a particle diameter of 200 nm in a quartz tube, placing the tube furnace, vacuuming the tube furnace, and introducing The Ar-supported gasified pyridine monomer (pyridine, 10 g) was used as a reaction gas, and the Ar gas was heated for 6 hours, and then cooled to room temperature to obtain a lithium ion secondary battery negative electrode active material.
  • pyridine 10 g
  • the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material.
  • the silicon-based active material is encapsulated inside the nitrogen-doped carbon material.
  • the silicon-based active material in the negative electrode active material of the lithium ion secondary battery is elemental silicon, and the mass ratio is 53.6% as measured by the ammonium chloride gravimetric method.
  • At least one of the surface and the interior of the nitrogen-doped carbon material has micropores, and the pore size distribution is between 20 and 50 nm by nitrogen adsorption method, calculated by BET and BJH.
  • nitrogen atoms exist in the form of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material includes a plurality of cross-linked branches having a diameter of about 300 to 500 nm.
  • 2 is a schematic view showing the structure of a nitrogen-doped carbon mesh in a negative active material of a lithium ion secondary battery produced in an embodiment of the present invention.
  • the nitrogen atom and the carbon atom in the nitrogen-doped carbon network are usually combined in various forms of a pyridine type nitrogen, a graphite type nitrogen, and a pyrrole type nitrogen.
  • a method for preparing a negative active material for a lithium ion secondary battery comprising the steps of: 5 g of an ionic liquid 3-mercapto-butylpyridinium salt (3 -methyl- 1 -buty lpyridine dicyanamide) in a dry atmosphere ) ⁇ ⁇ ⁇ lg lg lg lg lg lg lg 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • the lithium ion secondary battery anode active material includes a silicon-based active material and a nitrogen-doped carbon material.
  • the silicon-based active material is encapsulated inside the nitrogen-doped carbon material.
  • XRD analysis the silicon-based active material in the negative active material of lithium ion secondary battery is elemental silicon, which is determined by ammonium chloride gravimetric method. The amount ratio was 29.9%.
  • At least one of the surface and the interior of the nitrogen-doped carbon material has micropores, and the pore size distribution is 10 to 50 nm by nitrogen adsorption method, calculated by BET and BJH.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material includes a plurality of cross-linked branches having a diameter of about 100 to 200 nm.
  • the nitrogen atom exists in the form of pyridine type nitrogen, pyrrole type nitrogen and graphite nitrogen.
  • a method for preparing a negative electrode active material for a lithium ion secondary battery comprising the steps of: dissolving cetyltrimethylammonium bromide (CTAB, (C 16 H 33 )N(CH 3 ) 3 Br, 7.3 g ) In a solution of HCK 120 mL, 1 mol/L in an ice water bath, add 1 g of silicon powder with a particle size of 1 ⁇ m, ultrasonically disperse for 30 minutes, then add ammonium persulfate (APS, 13.7 g) to it immediately. A white suspension was formed and stirred for 0.5 hours.
  • CAB cetyltrimethylammonium bromide
  • APS ammonium persulfate
  • a pyrrole monomer (Py, 12 mL) was added to the suspension, and the reaction was kept at 4 ° C for 24 hours to form a black precipitate, which was filtered and used to obtain a filter residue.
  • 1 mol/L HCl solution was washed three times, then washed with pure water until the solution was colorless neutral, then the filter residue was dried at 80 ° C for 24 hours, and finally the dried filter residue was placed in a tube furnace, and passed.
  • a mixture of 5 % H 2 /Ar was sintered at 700 ° C for 2 hours to obtain a lithium ion secondary battery negative active material.
  • the silicon-based active material in the negative electrode active material of lithium ion secondary battery is elemental silicon, and its mass ratio is 28.3% as measured by ammonium chloride gravimetric method.
  • the pore size distribution is between 0.5 and 4 nm, as calculated by BET and BJH.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material includes a plurality of cross-linked branches, and the diameter of the branched skeleton is about 50 to 80 nm.
  • the nitrogen atom exists in the form of a pyridine type nitrogen and a pyrrole type nitrogen.
  • Comparative example three A method for preparing a negative active material for a lithium ion secondary battery, comprising the steps of: 5 g of an ionic liquid 3-mercapto-butylpyridine dicyanamide salt in a dry atmosphere
  • the silicon-based active material in the negative electrode active material of lithium ion secondary battery is elemental silicon, and its mass ratio is 31.9% as measured by ammonium chloride gravimetric method.
  • the pore size distribution of the pores was between 0.5 and 1 ⁇ m by the nitrogen adsorption method, calculated by BET and BJH.
  • the nitrogen-doped carbon material has a three-dimensional network, and the nitrogen-doped carbon material includes a plurality of cross-linked branches having a diameter of about 10 to 20 ⁇ m.
  • the nitrogen atom exists in the form of pyridine type nitrogen, pyrrole type nitrogen and graphitride nitrogen.
  • the lithium ion secondary battery anode active material prepared in the above first embodiment was uniformly mixed with a conductive agent (Timble, Super- and SFG-6), and then 8% polyvinylidene fluoride PVDF (Arkmer, HSV900), N was added.
  • a conductive agent TiAl, Super- and SFG-6
  • PVDF polyvinylidene fluoride
  • NMP - Nippopylpyrrolidone solution NMP, uniformly stirred, uniformly coating the above mixed slurry on a copper foil current collector of ⁇ , and baking at 110 ° C for 12 hours under vacuum to obtain a negative electrode sheet of a lithium ion secondary battery.
  • the lithium ion secondary battery negative electrode piece is made into a 2016 type button battery, wherein the counter electrode is made of lithium metal, the diaphragm is celgard C2400, and the electrolyte is 1.3M LiPF 6 of EC and DEC (volume ratio of 3:7) Solution.
  • Example 2 Example 2, Example 3, and lithium ion secondary electricity prepared in Comparative Example 1 to Comparative Example 3
  • the pool negative active material is treated as such.
  • effects are provided, for example, to evaluate the performance of the products provided by the embodiments of the present invention.
  • the button-type lithium ion secondary battery prepared in Example 1 to Example 3 and Comparative Example 1 to Comparative Example 3 was charged at a current of 100 mA / lg of active material to a voltage of 0.001 V, and then constant voltage until the current was less than 10 mA / Lg active substance; set aside for 10 min; discharge the above button cell with a current of 100 mA/lg of active material to 2.5 V.
  • the above charging and discharging process is recorded as one charging/discharging cycle.
  • the formulas for the first coulombic efficiency and capacity retention of the button-type lithium ion secondary battery are as follows, and the results are recorded in Table 1:
  • Capacity retention rate (%) at the nth cycle discharge capacity at the nth cycle / discharge capacity at the first cycle X 100%.
  • the lithium ion secondary battery negative electrode active material prepared by the negative electrode active material of the lithium ion secondary battery obtained in the first to third embodiments of the present invention and the comparative example at the same temperature The silicon/carbon composite has a relatively long cycle life, high capacity and first efficiency because the nitrogen-doped carbon network itself has a higher capacity and conductivity than carbon, while the nitrogen-doped carbon material has micropores. It can effectively reduce the influence of the volume change of the silicon-based active material on the overall life of the material.
  • the negative electrode active material of the lithium ion secondary battery prepared in the first embodiment to the third embodiment of the present invention is compared with the negative electrode active material of the lithium ion secondary battery prepared by the comparative examples 2 and 3 at the same temperature, and the silicon-based active material nano particles are compared.
  • the size is proportional to the diameter of the nitrogen-doped carbon material branch and the nitrogen-doped carbon material pore size distribution, and the conductivity is high, with higher capacity, first efficiency and cycle life.

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