WO2015165215A1 - 复合负极材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池 - Google Patents

复合负极材料及其制备方法、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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WO2015165215A1
WO2015165215A1 PCT/CN2014/088167 CN2014088167W WO2015165215A1 WO 2015165215 A1 WO2015165215 A1 WO 2015165215A1 CN 2014088167 W CN2014088167 W CN 2014088167W WO 2015165215 A1 WO2015165215 A1 WO 2015165215A1
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carbon
anode material
doping element
composite anode
lithium ion
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PCT/CN2014/088167
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English (en)
French (fr)
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夏圣安
李慧
谢封超
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华为技术有限公司
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Priority to EP14890939.3A priority Critical patent/EP3128585B1/en
Publication of WO2015165215A1 publication Critical patent/WO2015165215A1/zh
Priority to US15/339,081 priority patent/US10770720B2/en
Priority to US16/992,187 priority patent/US20200373566A1/en
Priority to US17/880,345 priority patent/US20220376235A1/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
    • H01M4/36—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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/36—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
    • 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

  • the present invention relates to the field of lithium ion secondary batteries, and in particular to a composite anode material and a preparation method thereof, a lithium ion secondary battery anode pole piece and a lithium ion secondary battery.
  • lithium battery graphite anode material has many advantages such as long cycle life, high efficiency, low cost, environmental friendliness and easy processing, the material has been widely used in portable electronic equipment, electric vehicles and energy storage.
  • the first aspect of the embodiments of the present invention provides a composite anode material having high capacity, low cost, long life and high rate charge and discharge characteristics, and the composite anode material can break through the theoretical capacity and rate limitation of the graphite anode.
  • an embodiment of the present invention provides a composite anode material including a carbon core layer and a carbon coating layer, wherein the carbon coating layer is a carbon layer coated on a surface of the carbon core. And characterized in that the carbon core contains a first doping element, and the first doping element is at least one of N, P, B, S, O, F, Cl, H elements.
  • the carbon coating layer comprises a second doping element
  • the second doping element is N, P, B, S, O, At least two of the F, Cl, and H elements, the first doping element and the second doping element may be the same or different.
  • the carbon coating layer occupies the carbon coating layer and the carbon Total mass of the prime kernel 5% to 30%.
  • the composite anode material is The doping element has a mass content of 0.1% to 50%.
  • the carbon core comprises at least one of natural graphite, artificial graphite, expanded graphite, graphite oxide, hard carbon, soft carbon, graphene, carbon nanotubes, and carbon fibers.
  • the embodiment of the invention provides a method for preparing the composite anode material according to any one of the first aspects:
  • an ionic liquid such as triphenylboron, 3-methyl-butylpyridine dicyanamide or 1-ethyl-3-methylimidazolium dicyanamide
  • the first mixture is placed in a tube furnace, and a mixed gas of a hydride containing a doping element and an inert carrier gas is introduced, and after calcination, a composite anode material can be obtained.
  • the mixed gas of the hydride containing the doping element and the inert carrier gas includes:
  • the ratio of the mixed gas of the hydride containing the doping element to the inert carrier gas is 5 to 100 ml/min, and the volume ratio of the hydride containing the doping element to the inert gas is 1:1 to 1:10;
  • the composite anode material can be obtained after the calcination comprises:
  • the composite anode material is obtained by raising the temperature in the tube furnace to 500 to 1000 ° C at a heating rate of 1 to 10 ° C / min and holding it for 0.5 to 12 hours, followed by cooling to room temperature.
  • the embodiment of the invention provides a method for preparing the composite anode material according to any one of the first aspects:
  • a composite anode material is prepared by introducing a mixed gas of a doping element-containing organic small molecule and an inert carrier gas into the tube furnace, and maintaining the temperature at 500 to 1000 ° C for 1 to 12 hours, wherein the composite anode material is obtained.
  • the organic small molecule includes one of pyridine, pyrrole, and thiophene.
  • the volume ratio of the doped element-containing hydride to the inert carrier gas is 1:1 to 1:10; the organic small molecule containing the doping element The volume ratio to the inert carrier gas is 1:1 to 1:10.
  • the embodiment of the invention provides a method for preparing the composite anode material according to any one of the first aspects:
  • a surfactant such as cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium carboxymethylcellulose
  • an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid
  • an oxidizing agent such as ammonium persulfate, ferric chloride, iron sulfate
  • the second mixed solution is subjected to an incubation reaction to obtain a black precipitate
  • the black precipitate is washed to neutrality and dried, and the dried black precipitate is placed in a tube furnace, and a mixed gas of a doped element-containing hydride and an inert carrier gas is introduced, and after sintering, The composite negative electrode material is obtained.
  • the insulating reaction of the second mixed solution to obtain a black precipitate specifically includes:
  • the second mixed solution is incubated at 0 to 4 ° C for 1 to 24 hours and then filtered to obtain a black precipitate;
  • the black precipitate is washed to neutrality and dried, and the dried black precipitate is placed in a tube furnace, and a mixed gas mixture of a hydride containing a doping element and an inert carrier gas is passed through
  • the composite anode material can be obtained after sintering, and specifically includes:
  • the black precipitate is washed with a hydrogen chloride solution to neutrality and dried at 50 to 100 ° C for 1 to 24 hours, and then the dried black precipitate is placed in a tube furnace, and a hydride containing a doping element is introduced. Combined with an inert carrier gas, sintering at 500 to 1000 ° C for 0.5 to 10 hours to produce a composite negative Extreme material.
  • 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 comprising a current collector and a composite negative electrode material coated on the current collector.
  • an embodiment of the present invention provides a lithium ion secondary battery, wherein the lithium ion secondary battery comprises a negative electrode tab of a lithium ion secondary battery, a positive electrode tab, a separator, a nonaqueous electrolyte, and
  • the outer casing is composed of a lithium ion secondary battery negative electrode tab including a current collector and a composite negative electrode material coated on the current collector.
  • the composite anode material provided by the first aspect of the present invention comprises a graphite core and a carbon coating layer, and both the graphite core and the carbon coating layer are doped with elements.
  • doping elements to form lattice defects in the carbon layer not only improves the fluid cloud mobility, but also reduces the anti-storage lithium barrier, increases the lithium-storage binding sites, and increases the interlayer spacing of the graphite carbon, greatly improving The lithium ion migration speed can break through the theoretical capacity of graphite of 372 mAh/g, thereby increasing the capacity and rate of the composite negative electrode material.
  • the method for preparing the composite anode material according to any one of the first aspects of the present invention, which is provided in the second aspect to the fourth aspect, is simple and convenient in process, low in cost, and easy to industrialize.
  • a lithium ion secondary battery negative electrode sheet provided by the fifth aspect of the present invention and a lithium ion secondary battery provided by the sixth aspect have a long service life and good electrical conductivity.
  • Example 1 is a SEM (scanning electron microscope) image of a composite negative electrode material prepared in Example 1 of the present invention
  • FIG. 2 is a cycle diagram of charging and discharging of a button battery at different magnifications according to Embodiment 1 of the present invention
  • Embodiment 3 is an XPS (X-ray Photoelectron Spectroscopy) spectrum of a composite anode material in different states of charge according to Embodiment 1 of the present invention.
  • the first aspect of the embodiment of the present invention provides a composite anode material, which solves the problem that the rate of magnification is difficult to be improved and the capacity is close to the limit in the prior art.
  • the second to fourth aspects of the embodiments of the present invention provide the method for preparing the composite anode material according to the first aspect, which is simple and convenient in process, low in cost, and easy to industrialize.
  • a fifth aspect of the present invention provides a lithium ion secondary battery negative electrode sheet comprising the composite negative electrode material according to the first aspect, and a sixth aspect of the present invention provides the composite negative electrode according to the first aspect. Materials for lithium ion secondary batteries.
  • an embodiment of the present invention provides a composite anode material including a carbon core layer and a carbon coating layer, wherein the carbon coating layer is a carbon layer coated on a surface of the carbon core. And characterized in that the carbon core contains a first doping element, and the first doping element is at least one of N, P, B, S, O, F, Cl, H elements.
  • the carbon coating layer includes a second doping element, and the second doping element is at least two of N, P, B, S, O, F, Cl, and H elements, the first The doping element may or may not be the same as the second doping element.
  • the carbon coating layer has a mass of 5% to 30% of the total mass of the carbon coating layer and the carbon core.
  • the doping element in the composite anode material has a mass content of 0.1% to 50%.
  • the carbon core comprises at least one of natural graphite, artificial graphite, expanded graphite, graphite oxide, hard carbon, soft carbon, graphene, carbon nanotubes, and carbon fibers.
  • a first aspect of the present invention provides a composite anode material comprising a graphite core and a carbon coating layer, and element doping in both the graphite core and the carbon coating layer.
  • the use of doping elements to form lattice defects in the carbon layer not only improves the fluid cloud mobility, but also reduces the anti-storage lithium barrier, increases the lithium-storage binding sites, and increases the interlayer spacing of the graphite carbon, greatly improving Lithium ion migration rate, and can break through the theoretical capacity of graphite 372mAh / g (mA / gram), thereby improving the composite anode material Capacity and rate.
  • the embodiment of the invention provides the preparation method of the composite anode material according to the first aspect, which is prepared according to one of the following methods:
  • an ionic liquid such as triphenylboron, 3-methyl-butylpyridine dicyanamide or 1-ethyl-3-methylimidazolium dicyanamide
  • the first mixture is placed in a tube furnace, and a mixed gas of a hydride containing a doping element and an inert carrier gas is introduced, and after calcination, a composite anode material can be obtained.
  • the ionic liquid and the carbon material are mixed and oscillated for 30 to 120 minutes, and the mixed gas of the hydride containing the doping element and the inert carrier gas is 5 to 100 ml/ Min, the volume ratio of the hydride containing the doping element to the inert gas is 1:1 to 1:10;
  • the composite anode material can be obtained after the calcination comprises:
  • the composite anode material is obtained by raising the temperature in the tube furnace to 500 to 1000 ° C at a heating rate of 1 to 10 ° C / min and holding it for 0.5 to 12 hours, followed by cooling to room temperature.
  • Method 2 Put the carbon material into the tube furnace
  • a composite anode material is prepared by introducing a mixed gas of a doping element-containing organic small molecule and an inert carrier gas into the tube furnace, and maintaining the temperature at 500 to 1000 for 1 to 12 hours, wherein the organic anode material is obtained.
  • Small molecules include one of pyridine, pyrrole, and thiophene.
  • the volume ratio of the hydride containing dopant element to the inert carrier gas is 1:1 to 1:10; the volume ratio of the organic small molecule containing the doping element to the inert carrier gas is 1: 1 to 1:10.
  • a surfactant such as cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium carboxymethylcellulose
  • an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid
  • an oxidizing agent such as ammonium persulfate, ferric chloride, iron sulfate
  • the second mixed solution is subjected to an incubation reaction to obtain a black precipitate
  • the black precipitate is washed to neutrality and dried, and the dried black precipitate is placed in a tube furnace, and a mixed gas of a doped element-containing hydride and an inert carrier gas is introduced, and after sintering, The composite negative electrode material is obtained.
  • the second mixed solution is subjected to a heat preservation reaction, and the black precipitate is obtained, which specifically includes:
  • the second mixed solution is incubated at 0 to 4 ° C for 1 to 24 hours and then filtered to obtain a black precipitate;
  • the black precipitate is washed to neutrality and dried, and the dried black precipitate is placed in a tube furnace, and a mixed gas mixture of a hydride containing a doping element and an inert carrier gas is passed through
  • the composite anode material can be obtained after sintering, and specifically includes:
  • the black precipitate is washed with a hydrogen chloride solution to neutrality and dried at 50 to 100 ° C for 1 to 24 hours, and then the dried black precipitate is placed in a tube furnace, and a hydride containing a doping element is introduced.
  • the composite negative electrode material can be obtained by sintering at 500 to 1000 ° C for 0.5 to 10 hours with a mixed gas of an inert carrier gas.
  • the method for preparing a negative electrode 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 lithium ion secondary battery negative electrode tab, the lithium ion secondary battery negative electrode tab including a current collector and a composite negative electrode material coated on the current collector.
  • a lithium ion secondary battery negative electrode sheet provided by the third aspect of the present invention has a long service life and good electrical conductivity.
  • the lithium ion secondary battery anode active material is as described in 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 current collector and a composite negative electrode material coated on the current collector.
  • the lithium ion secondary battery provided by the fourth aspect of the embodiment of the present invention has a long service life and good electrical conductivity.
  • the lithium ion secondary battery anode active material is as described in the first aspect.
  • a method for preparing a composite anode material comprising the steps of:
  • C16H33 cetyltrimethylammonium bromide
  • HCl 120mL, 1mol/L
  • APS ammonium persulfate
  • pyrrole monomer Pyrrole, 8.3 mL was further added, and the reaction was kept at 4 ° C for 24 hours.
  • a composite anode material was obtained by passing a 10% N2H4/Ar mixture gas and sintering at 700 ° C for 5 hours.
  • Fig. 1 is a SEM (scanning electron microscope) chart of the composite negative electrode material.
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • FIG. 2 is a charge and discharge cycle diagram of the obtained button battery at different currents, the 1C capacity reaches 460 mAh/g, and the 30C capacity retention rate is 50%.
  • FIG. 3 is an XPS (X-ray Photoelectron Spectroscopy) spectrum of the composite anode material under different states of charge. It can be seen from the figure that the N1s peak can be fitted before lithium insertion. The three sub-peaks at 398.2, 399.7 and 401.2eV are assigned to pyridine, pyrrole and graphite-N. When the electrode is fully intercalated, the peak position of pyridine-N shifts to 387.5 eV, indicating the oxidation state of pyridine-N. It becomes more negative, so the bond energy can be lowered. The displacement of the peak proves that pyridine-N combines with Li+ to form a bond.
  • XPS X-ray Photoelectron Spectroscopy
  • a method for preparing a composite anode material comprising the steps of:
  • C16H33 cetyltrimethylammonium bromide
  • HCl 120mL, 1mol/L
  • APS ammonium persulfate
  • pyrrole monomer Pyrrole, 8.3 mL was further added, and the reaction was kept at 4 ° C for 24 hours.
  • the obtained black precipitate was washed three times with 1 mol/L HCl solution, and then washed with purified water until the solution was colorless neutral, and then the precipitate was dried at 80 ° C for 24 h, and finally the dried precipitate was placed.
  • a 15% PH3/Ar mixture was introduced, the flow rate was controlled to 20 ml/min, and the temperature in the tube furnace was raised to 700 ° C at a heating rate of 2 ° C / min and held for 5 hours to obtain a composite negative electrode. material.
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 620 mAh/g, and the 30C capacity retention rate was 43%.
  • a method for preparing a composite anode material comprising the steps of:
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 510 mAh/g, and the 30C capacity retention rate was 44%.
  • a method for preparing a composite anode material comprising the steps of:
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 540 mAh/g, and the 30C capacity retention rate was 51%.
  • a method for preparing a composite anode material comprising the steps of:
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 420 mAh/g, and the 30C capacity retention rate was 42%.
  • a method for preparing a composite anode material comprising the steps of:
  • 3g of natural graphite was placed in a tube furnace, and the tube furnace was evacuated.
  • Ar-loaded gasified BCl3 (4:1 v/v) was used as the reaction gas.
  • the flow rate of Ar was controlled to 250 ml/min to 30 °C/
  • the heating rate of min increased the temperature in the tube furnace to 800 ° C and kept it for 3 hours, and then introduced Ar gas-loaded pyridine monomer (5:1 v/v) as the reaction gas, and the Ar flow rate was controlled to 50 ml/min. And keep it for 6 hours, until the tube furnace is cooled to room temperature, you can A composite anode material is obtained.
  • the prepared composite anode active material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C in vacuum.
  • the electrode sheets were then assembled into a button cell in a glove box for testing, wherein the counter electrode was lithium metal, the diaphragm was celgard C2400, and the electrolyte was 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 450 mAh / g, 30C capacity retention rate of 20%.
  • a method for preparing a composite anode material comprising the steps of:
  • 3g artificial graphite was placed in a tube furnace, and the tube furnace was evacuated.
  • Ar-loaded gasified pyrrole monomer (5:1 v/v) was introduced as a reaction gas, and the Ar flow rate was controlled to 50 ml/min to 30.
  • the temperature rise rate of °C/min raises the temperature in the tube furnace to 800 ° C and keeps it for 6 hours, then passes 25% PH3/Ar, the flow rate is controlled to 100 ml/min, and is kept for 4 hours.
  • the tube furnace is cooled to room temperature. , the composite anode material can be obtained.
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 430 mAh / g, 30C capacity retention rate of 25%.
  • the prepared composite anode material is uniformly coated on a copper foil current collector by mixing with conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 85:10:5, and dried at 120 ° C to obtain an electrode.
  • the sheets were then assembled into a glove cell in a glove box for lithium metal, the separator was celgard C2400, and the electrolyte was a 1.3 M LiPF6 EC and DEC (3:7 by volume) solution.
  • the obtained button battery 1C capacity reached 365 mAh/g, and the 30C capacity retention rate was 5%.
  • the actual capacity of the composite negative electrode material breaks through the traditional stone.
  • the theoretical capacity of the ink negative electrode material (currently 372 mAh / g), and greatly improve the rapid charge and discharge capacity of the graphite material.
  • the effect embodiment is to strongly support the beneficial effects of the embodiments of the present invention, and provides an effect implementation, for example, to evaluate the performance of the product provided by the embodiment of the present invention.
  • the composite negative electrode material has high capacity and rapid charge and discharge capability compared with the carbon-coated graphite negative electrode material prepared in the comparative example at the same temperature.
  • Doping elements form lattice defects in the carbon layer, which not only can improve the flow of electron clouds, but also reduce the barrier of anti-storage lithium, increase the lithium-binding sites, increase the interlayer spacing of graphite carbon, and greatly improve lithium. Ion migration rate, and can break through the theoretical capacity of graphite 372mAh / g.

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Abstract

一种复合负极材料，包括碳素内核和碳包覆层，所述碳包覆层为包覆在所述碳素内核表面的碳层，其特征在于，所述碳素内核和所述碳包覆层中均包含掺杂元素，所述掺杂元素为N、P、B、S、O、F、Cl、H元素中至少一种。还提供了复合负极材料的制备方法、包含复合负极材料的锂离子二次电池负极极片以及包含锂离子二次电池负极活性材料的锂离子二次电池。

Description

复合负极材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池 技术领域
本发明涉及锂离子二次电池领域，特别是涉及一种复合负极材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池。
背景技术
由于锂电池石墨负极材料具有循环寿命长、首效高、成本低、环境友好、易加工等多种优点，使得该材料已经在便携电子设备、电动车和储能领域得到广泛应用。
但石墨的理论比容量较低(约372毫安时/克)，与电解液相容性差、倍率特性不好，通过碳包覆技术，使得石墨与电解液的相容性得到了改善，但其倍率性一直难以提高，而且容量已接近极限。
发明内容
有鉴于此，本发明实施例第一方面提供了一种具有高容量、低成本、长寿命和高倍率充放电特性的复合负极材料，该复合负极材料能够突破石墨负极的理论容量和倍率限制。
第一方面，本发明实施例提供了一种复合负极材料，所述复合负极材料包括碳素内核和碳包覆层，所述碳包覆层为包覆在所述碳素内核表面的碳层，其特征在于，所述碳素内核中包含第一掺杂元素，所述第一掺杂元素为N、P、B、S、O、F、Cl、H元素中至少一种。
结合第一方面，在第一方面的第一种可实现的方式中，所述碳包覆层包含第二掺杂元素，所述第二掺杂元素为N、P、B、S、O、F、Cl、H元素中至少两种，所述第一掺杂元素与所述第二掺杂元素可以相同也可以不相同。
结合第一方面或第一方面的第一种可实现的方式，在第一方面的第二种可实现的方式中，所述碳包覆层的质量占所述碳包覆层和所述碳素内核的总质量的 5％至30％。
结合第一方面或第一方面的第一种可实现的方式或第一方面的第二种可实现的方式，在第一方面的第三种可实现的方式中，所述复合负极材料中所述掺杂元素的质量含量为0.1％至50％。
结合第一方面或第一方面的第一种可实现的方式或第一方面的第二种可实现的方式中或第一方面的第三种可实现的方式，在第一方面的第四种可实现的方式中，所述碳素内核包括天然石墨、人造石墨、膨胀石墨、氧化石墨、硬碳、软碳、石墨烯、碳纳米管、碳纤维中的至少一种。
第二方面，本发明实施例提供了一种用于制备第一方面任一项所述的复合负极材料的方法：
将离子液体(如三苯基硼、3-甲基-丁基吡啶二氰胺盐或1-乙基-3-甲基咪唑二氰胺)与碳素材料进行混合震荡，获得第一混合物；
将所述第一混合物放入管式炉内，通入含掺杂元素的氢化物与惰性载气的混合气体，经过煅烧后即可制得复合负极材料。
结合第二方面，在第二方面的第一种可能的实现方式中，
将离子液体与碳素材料进行混合震荡的时间为30至120分钟，
所述通入含掺杂元素的氢化物与惰性载气的混合气体包括：
通入含掺杂元素的氢化物与惰性载气的混合气体的速率为5至100ml/min，含掺杂元素的氢化物与惰性气体的体积比为1：1至1：10；
所述经过煅烧后即可制得复合负极材料具体包括：
以1至10℃/min的升温速率将管式炉内升温至500至1000℃并保温0.5至12小时，随后冷却至室温，即可得到复合负极材料。
第三方面，本发明实施例提供了一种用于制备第一方面任一项所述的复合负极材料的方法：
将碳素材料放入管式炉内；
将所述管式炉抽真空，向所述管式炉内通入含掺杂元素的氢化物与惰性载气的混合气体，并在500至1000℃的温度下保温1至12小时；
向所述管式炉内通入含掺杂元素的有机小分子与惰性载气的混合气体，在500至1000℃的温度下保温1至12小时即可制得复合负极材料，其中，所述有机小分子包括吡啶、吡咯、噻吩中的一种。
结合第三方面，在第三方面的第一种可能的实现方式中，含掺杂元素的氢化物与惰性载气的体积比为1：1至1：10；含掺杂元素的有机小分子与惰性载气的体积比为1：1至1：10。
第四方面，本发明实施例提供了一种用于制备第一方面任一项所述的复合负极材料的方法：
将表面活性剂(如十六烷基三甲基溴化铵、十二烷基苯磺酸钠、羧甲基纤维素钠)溶解在酸(如盐酸、硫酸、硝酸、磷酸)中制得第一混合溶液；
将碳素材料超生分散在所述第一混合溶液中，并加入氧化剂(如过硫酸铵、三氯化铁、硫酸铁)获得悬浊液；
向所述悬浊液中加入吡咯单体制得第二混合溶液；
将所述第二混合溶液进行保温反应，获得黑色沉淀物；
将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，经过烧结后即可制得所述复合负极材料。
结合第四方面，在第四方面的第一种可能的实现方式中，
所述将所述第二混合溶液进行保温反应，获得黑色沉淀物具体包括：
将所述第二混合溶液在0至4℃下保温反应1至24h后过滤，获得黑色沉淀物；
所述将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体混合气，经过烧结后即可制得复合负极材料具体包括：
将所述黑色沉淀物用氯化氢溶液洗涤至中性并在50至100℃下干燥1至24小时，然后将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，在500至1000℃下烧结0.5至10小时即可制得复合负 极材料。
第五方面，本发明实施例提供了一种锂离子二次电池负极极片，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的复合负极材料。
第六方面，本发明实施例提供了一种锂离子二次电池，其特征在于，所述锂离子二次电池由锂离子二次电池负极极片、正极极片、隔膜、非水电解液和外壳组成，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的复合负极材料。
从上可知，本发明实施例第一方面提供的复合负极材料包含石墨内核和碳包覆层，且石墨内核和碳包覆层中均有元素掺杂。利用掺杂元素在碳层中形成晶格缺陷，不仅可以提高电子云流动性，而且还能降低反储锂应势垒、增加储锂结合位点、增加石墨碳的层间距，大大地提高了锂离子迁移速度，并能突破石墨的理论容量372mAh/g，从而提升了所述复合负极材料容量和倍率性。本发明实施例第二方面至第四方面提供的如第一方面任一项所述的复合负极材料的制备方法工艺简单方便，成本低，易于工业化生产。本发明实施例第五方面提供的一种锂离子二次电池负极极片和第六方面提供的锂离子二次电池使用寿命长且电导率良好。
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例一制得的复合负极材料的SEM(scanning electron microscope，扫描式电子显微镜)图；
图2为本发明实施例一中扣式电池在不同倍率下充放电循环图；
图3为本发明实施例一中复合负极材料在不同充电状态下的XPS(X-ray Photoelectron Spectroscopy，X射线光电子能谱)谱。
具体实施方式
以下所述是本发明实施例可选的实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
本发明实施例第一方面提供了一种复合负极材料，解决了现有技术中倍率性难以提高、容量已接近极限的问题。本发明实施例第二方面至第四方面提供了如第一方面所述的复合负极材料的制备方法，工艺简单方便，成本低，易于工业化生产。本发明实施例第五方面提供了包含如第一方面所述的复合负极材料的锂离子二次电池负极极片，以及本发明实施例第六方面提供了包含如第一方面所述的复合负极材料的锂离子二次电池。
第一方面，本发明实施例提供了一种复合负极材料，所述复合负极材料包括碳素内核和碳包覆层，所述碳包覆层为包覆在所述碳素内核表面的碳层，其特征在于，所述碳素内核中包含第一掺杂元素，所述第一掺杂元素为N、P、B、S、O、F、Cl、H元素中至少一种。
可选的，所述碳包覆层包含第二掺杂元素，所述第二掺杂元素为N、P、B、S、O、F、Cl、H元素中至少两种，所述第一掺杂元素与所述第二掺杂元素可以相同也可以不相同。
可选的，所述碳包覆层的质量占所述碳包覆层和所述碳素内核的总质量的5％至30％。
可选的，所述复合负极材料中所述掺杂元素的质量含量为0.1％至50％。
可选的，所述碳素内核包括天然石墨、人造石墨、膨胀石墨、氧化石墨、硬碳、软碳、石墨烯、碳纳米管、碳纤维中的至少一种。
本发明实施例第一方面提供了一种复合负极材料，该复合负极材料包含石墨内核和碳包覆层，且石墨内核和碳包覆层中均有元素掺杂。利用掺杂元素在碳层中形成晶格缺陷，不仅可以提高电子云流动性，而且还能降低反储锂应势垒、增加储锂结合位点、增加石墨碳的层间距，大大地提高了锂离子迁移速度，并能突破石墨的理论容量372mAh/g(毫安时/克)，从而提升了该复合负极材料 容量和倍率性。
第二方面，本发明实施例提供了第一方面所述的复合负极材料的制备方法，按以下方法中的一种进行制备：
方法一：
将离子液体(如三苯基硼、3-甲基-丁基吡啶二氰胺盐或1-乙基-3-甲基咪唑二氰胺)与碳素材料进行混合震荡，获得第一混合物；
将所述第一混合物放入管式炉内，通入含掺杂元素的氢化物与惰性载气的混合气体，经过煅烧后即可制得复合负极材料。
可选的，在方法一中，将离子液体与碳素材料进行混合震荡的时间为30至120分钟，通入含掺杂元素的氢化物与惰性载气的混合气体的速率为5至100ml/min，含掺杂元素的氢化物与惰性气体的体积比为1：1至1：10；
所述经过煅烧后即可制得复合负极材料具体包括：
以1至10℃/min的升温速率将管式炉内升温至500至1000℃并保温0.5至12小时，随后冷却至室温，即可得到复合负极材料。
方法二:将碳素材料放入管式炉内；
将所述管式炉抽真空，向所述管式炉内通入含掺杂元素的氢化物与惰性载气的混合气体，并在500至1000度的温度下保温1至12小时；
向所述管式炉内通入含掺杂元素的有机小分子与惰性载气的混合气体，在500至1000的温度下保温1至12小时即可制得复合负极材料，其中，所述有机小分子包括吡啶、吡咯、噻吩中的一种。
可选的，在方法二中，含掺杂元素的氢化物与惰性载气的体积比为1：1至1：10；含掺杂元素的有机小分子与惰性载气的体积比为1：1至1：10。
方法三：
将表面活性剂(如十六烷基三甲基溴化铵、十二烷基苯磺酸钠、羧甲基纤维素钠)溶解在酸(如盐酸、硫酸、硝酸、磷酸)中制得第一混合溶液；
将碳素材料超生分散在所述第一混合溶液中，并加入氧化剂(如过硫酸铵、三氯化铁、硫酸铁)获得悬浊液；
向所述悬浊液中加入吡咯单体制得第二混合溶液；
将所述第二混合溶液进行保温反应，获得黑色沉淀物；
将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，经过烧结后即可制得所述复合负极材料。
可选的，在方法三中，所述将所述第二混合溶液进行保温反应，获得黑色沉淀物具体包括：
将所述第二混合溶液在0至4℃下保温反应1至24h后过滤，获得黑色沉淀物；
所述将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体混合气，经过烧结后即可制得复合负极材料具体包括：
将所述黑色沉淀物用氯化氢溶液洗涤至中性并在50至100℃下干燥1至24小时，然后将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，在500至1000℃下烧结0.5至10小时即可制得复合负极材料。
本发明实施例第二方面提供的一种锂离子二次电池负极活性材料的制备方法工艺简单方便，成本低，易于工业化生产。
第三方面，本发明实施例提供了一种锂离子二次电池负极极片，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的复合负极材料。本发明实施例第三方面提供的一种锂离子二次电池负极极片使用寿命长且电导率良好。其中所述锂离子二次电池负极活性材料如第一方面所述。
第四方面，本发明实施例提供了一种锂离子二次电池，所述锂离子二次电池由锂离子二次电池负极极片、正极极片、隔膜、非水电解液和外壳组成，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的复合负极材料。本发明实施例第四方面提供的锂离子二次电池使用寿命长且电导率良好。其中所述锂离子二次电池负极活性材料如第一方面所述。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
实施例一
一种复合负极材料的制备方法，包括以下步骤：
将十六烷基三甲基溴化铵(CTAB，(C16H33)N(CH3)3Br，7.3g)溶解在冰水浴的HCl(120mL，1mol/L)溶液中，再加入10g天然石墨，超生分散30分钟，然后将过硫酸铵(APS，13.7g)加入其中，立刻形成白色的悬浊液，搅拌0.5小时后，再加入吡咯单体(Pyrrole，8.3mL)，在4℃下保温反应24h后过滤，将得到的黑色沉淀物用1mol/L的HCl溶液洗涤三次，再用纯净水洗涤至溶液呈无色中性，接着把沉淀物在80℃下干燥24h，最后将干燥后的沉淀物放置在管式炉中，通入10％N2H4/Ar混合气，在700℃下烧结5小时即可得到复合负极材料。图1为该复合负极材料的SEM(scanning electron microscope，扫描式电子显微镜)图。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。
如图2所示，图2为所得扣式电池的在不同电流下的充放电循环图，1C容量达到460mAh/g，30C容量保持率50％。
如图3所示，图3为复合负极材料在不同充电状态下的XPS(X-ray Photoelectron Spectroscopy，X射线光电子能谱)谱，从图中可以看出，嵌锂之前N1s峰可拟合成位于398.2、399.7和401.2eV的三个亚峰，分别归属于吡啶、吡咯和石墨-N，当电极全嵌锂后，吡啶-N的峰位移动到387.5eV，这表明吡啶-N的氧化态变得更负，因此键能降低，该峰的位移证明了吡啶-N与Li+结合成键，再完全脱锂后，吡啶-N的峰位又回到初始位置，这表明Li+几乎完全从原来的吡啶-N位置脱离。以上现象证明Li+能可逆的与N-活化的位点键合，尤其是吡啶-N的位点。
实施例二
一种复合负极材料的制备方法，包括以下步骤：
将十六烷基三甲基溴化铵(CTAB，(C16H33)N(CH3)3Br，7.3g)溶解在冰水浴的HCl(120mL，1mol/L)溶液中，再加入10g人造石墨，超生分散30分钟，然后将过硫酸铵(APS，13.7g)加入其中，立刻形成白色的悬浊液，搅拌0.5小时后，再加入吡咯单体(Pyrrole，8.3mL)，在4℃下保温反应24h后过滤，将得到的黑色沉淀物用1mol/L的HCl溶液洗涤三次，再用纯净水洗涤至溶液呈无色中性，接着把沉淀物在80℃下干燥24h，最后将干燥后的沉淀物放置在管式炉中，通入15％PH3/Ar混合气，流量控制为20ml/min，以2℃/min的升温速率将管式炉内升温至700℃并保温5小时，即可得到复合负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到620mAh/g，30C容量保持率43％。
实施例三
一种复合负极材料的制备方法，包括以下步骤：
在干燥气氛下，将5g三苯基硼与1g膨胀石墨均匀混合后，在震荡混合其中震荡60min，将混合物转入到坩埚中放入管式炉内，通入30％NH3/Ar混合气，流量控制为10ml/min，以2℃/min的升温速率将管式炉内升温至800℃并保温6小时，再通入Ar负载气化的噻吩单体(4:1v/v)做反应气，Ar流量控制为250ml/min，保温3小时，随后冷却至室温，即可得到复合负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到510mAh/g，30C容量保持率44％。
实施例四
一种复合负极材料的制备方法，包括以下步骤：
在干燥气氛下，将5g三苯基硼与1g膨胀石墨均匀混合后，在震荡混合其中震荡60min，将混合物转入到坩埚中放入管式炉内，通入30％NH3/Ar混合气，流量控制为10ml/min，以2℃/min的升温速率将管式炉内升温至800℃并保温6小时，随后冷却至室温，即可得到复合负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到540mAh/g，30C容量保持率51％。
实施例五
一种复合负极材料的制备方法，包括以下步骤：
在干燥气氛下，将5g三苯基硼与1g硬碳均匀混合后，在震荡混合其中震荡60min，将混合物转入到坩埚中放入管式炉内，通入10％H2S/Ar混合气，流量控制为30ml/min，以2℃/min的升温速率将管式炉内升温至600℃并保温4小时，随后冷却至室温，即可得到复合负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到420mAh/g，30C容量保持率42％。
实施例六
一种复合负极材料的制备方法，包括以下步骤：
将3g天然石墨放入管式炉内，将管式炉抽真空，先通入Ar负载气化的BCl3(4:1v/v)做反应气，Ar流量控制为250ml/min，以30℃/min的升温速率将管式炉内的温度升到800℃并保温3小时，再通入Ar负载气化的吡啶单体(5:1v/v)做反应气，Ar流量控制为50ml/min，并保温6小时，待管式炉冷却至室温，即可 得到复合负极材料。
将制备得到的复合负极活性材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到450mAh/g，30C容量保持率20％。
实施例七
一种复合负极材料的制备方法，包括以下步骤：
将3g人造石墨放入管式炉内，将管式炉抽真空，先通入Ar负载气化的吡咯单体(5:1v/v)做反应气，Ar流量控制为50ml/min，以30℃/min的升温速率将管式炉内的温度升到800℃并保温6小时，再通入25％PH3/Ar，流量控制为100ml/min，并保温4小时，待管式炉冷却至室温，即可得到复合负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到430mAh/g，30C容量保持率25％。
对比例一
把3g天然石墨放入管式炉内，将管式炉抽真空，通入Ar/甲烷(体积比为8：2)做反应气，气流量控制为50ml/min，以30℃/min的升温速率将管式炉内的温度升到700℃并保温6小时，待管式炉冷却至室温，碳包覆石墨负极材料。
将制备得到的复合负极材料按照质量比85：10：5与导电炭黑、聚偏二氟乙烯在N-甲基吡咯烷酮中混合均匀涂于铜箔集流体上，120℃真空烘干，得到电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC和DEC(体积比为3:7)溶液。所得扣式电池1C容量达到365mAh/g，30C容量保持率5％。
根据实施例七与对比例一可知，该复合负极材料的实际容量突破了传统石 墨负极材料的理论容量(目前为372mAh/g)，并大大提高了石墨材料的快速充放电能力。
效果实施例为有力支持本发明实施例的有益效果，提供效果实施例如下，用以评测本发明实施例提供的产品的性能。
从本发明实施例一至实施例七可知，制得复合负极材料与同等温度下的对比例一制得的碳包覆石墨负极材料相比，具有高的容量和快速充放电的能力，这是因为掺杂元素在碳层中形成晶格缺陷，不仅可以提高电子云流动性，而且还能降低反储锂应势垒、增加储锂结合位点、增加石墨碳的层间距，大大地提高了锂离子迁移速度，并能突破石墨的理论容量372mAh/g。

Claims (13)

  1. 一种复合负极材料，所述复合负极材料包括碳素内核和碳包覆层，所述碳包覆层为包覆在所述碳素内核表面的碳层，其特征在于，所述碳素内核中包含第一掺杂元素，所述第一掺杂元素为N、P、B、S、O、F、Cl、H元素中至少一种。
  2. 如权利要求1所述的复合负极材料，其特征在于，所述碳包覆层包含第二掺杂元素，所述第二掺杂元素为N、P、B、S、O、F、Cl、H元素中至少两种，所述第一掺杂元素与所述第二掺杂元素可以相同也可以不相同。
  3. 如权利要求1或2所述的复合负极材料，其特征在于，所述碳包覆层的质量占所述碳包覆层和所述碳素内核的总质量的5％至30％。
  4. 如权利要求1至3任一所述的复合负极材料，其特征在于，所述复合负极材料中所述掺杂元素的质量含量为0.1％至50％。
  5. 如权利要求1至4任一所述的复合负极材料，其特征在于，所述碳素内核包括天然石墨、人造石墨、膨胀石墨、氧化石墨、硬碳、软碳、石墨烯、碳纳米管、碳纤维中的至少一种。
  6. 一种用于制备权1至权5任一项所述的复合负极材料的方法，其特征在于，
    将离子液体(如三苯基硼、3-甲基-丁基吡啶二氰胺盐或1-乙基-3-甲基咪唑二氰胺)与碳素材料进行混合震荡，获得第一混合物；
    将所述第一混合物放入管式炉内，通入含掺杂元素的氢化物与惰性载气的混合气体，经过煅烧后即可制得复合负极材料。
  7. 如权利要求6所述的方法，其特征在于，将离子液体与碳素材料进行混合震荡的时间为30至120分钟，
    所述通入含掺杂元素的氢化物与惰性载气的混合气体包括：
    通入含掺杂元素的氢化物与惰性载气的混合气体的速率为5至100ml/min，含掺杂元素的氢化物与惰性气体的体积比为1：1至1：10；
    所述经过煅烧后即可制得复合负极材料具体包括：
    以1至10℃/min的升温速率将管式炉内升温至500至1000℃并保温0.5至12小时，随后冷却至室温，即可得到复合负极材料。
  8. 一种用于制备权1至权5任一项所述的复合负极材料的方法，其特征在于，
    将碳素材料放入管式炉内；
    将所述管式炉抽真空，向所述管式炉内通入含掺杂元素的氢化物与惰性载气的混合气体，并在500至1000℃的温度下保温1至12小时；
    向所述管式炉内通入含掺杂元素的有机小分子与惰性载气的混合气体，在500至1000℃的温度下保温1至12小时即可制得复合负极材料，其中，所述有机小分子包括吡啶、吡咯、噻吩中的一种。
  9. 如权利要求8所述的方法，其特征在于，含掺杂元素的氢化物与惰性载气的体积比为1：1至1：10；含掺杂元素的有机小分子与惰性载气的体积比为1：1至1：10。
  10. 一种用于制备权1至权5任一项所述的复合负极材料的方法，其特征在于，
    将表面活性剂(如十六烷基三甲基溴化铵、十二烷基苯磺酸钠、羧甲基纤维素钠)溶解在酸(如盐酸、硫酸、硝酸、磷酸)中制得第一混合溶液；
    将碳素材料超生分散在所述第一混合溶液中，并加入氧化剂(如过硫酸铵、三氯化铁、硫酸铁)获得悬浊液；
    向所述悬浊液中加入吡咯单体制得第二混合溶液；
    将所述第二混合溶液进行保温反应，获得黑色沉淀物；
    将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，经过烧结后即可制得所述复合负极材料。
  11. 如权利要求10所述的方法，其特征在于，
    所述将所述第二混合溶液进行保温反应，获得黑色沉淀物具体包括：
    将所述第二混合溶液在0至4℃下保温反应1至24h后过滤，获得黑色沉 淀物；
    所述将所述黑色沉淀物洗涤至中性并进行干燥，将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体混合气，经过烧结后即可制得复合负极材料具体包括：
    将所述黑色沉淀物用氯化氢溶液洗涤至中性并在50至100℃下干燥1至24小时，然后将干燥后的黑色沉淀物放置在管式炉中，通入含掺杂元素的氢化物与惰性载气的混合气体，在500至1000℃下烧结0.5至10小时即可制得复合负极材料。
  12. 一种锂离子二次电池负极极片，其特征在于，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的权1至权5任一项所述的复合负极材料。
  13. 一种锂离子二次电池，其特征在于，所述锂离子二次电池由锂离子二次电池负极极片、正极极片、隔膜、非水电解液和外壳组成，所述锂离子二次电池负极极片包括集流体和涂覆在所述集流体上的权1至权5任一项所述的复合负极材料。
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