WO2023245967A1 - 一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用 - Google Patents

一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用 Download PDF

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WO2023245967A1
WO2023245967A1 PCT/CN2022/131834 CN2022131834W WO2023245967A1 WO 2023245967 A1 WO2023245967 A1 WO 2023245967A1 CN 2022131834 W CN2022131834 W CN 2022131834W WO 2023245967 A1 WO2023245967 A1 WO 2023245967A1
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negative electrode
hard carbon
interface
carbon negative
modified
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French (fr)
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陈卫华
宋轲铭
薛明昊
李文斌
盖晶晶
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郑州大学
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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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—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
    • H01M4/139—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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 invention belongs to the technical field of sodium-ion batteries, relates to the preparation of hard carbon negative electrodes, and specifically relates to an interface-modified sodium-ion battery hard carbon negative electrode material/negative electrode, preparation method and application.
  • sodium-ion batteries are regarded as one of the most promising next-generation energy storage systems due to their abundant resource reserves and low cost.
  • existing sodium-ion battery technology cannot meet the current society's needs for large-scale energy storage power stations and new energy trams. Therefore, the development of sodium-ion batteries with low cost, high energy density, high power density and long cycle life has become an urgent need.
  • Hard carbon has been widely studied due to its low sodium storage voltage (about 0.1V) and high storage capacity, and has been applied to sodium-ion battery anode materials, and has become the main candidate anode material in the commercialization of sodium-ion batteries.
  • Most hard carbons that can be produced on a large scale show low specific capacity and poor rate performance.
  • sodium-ion batteries have price advantages, they do not show high electrochemical performance, which is a challenge for hard carbon materials. Application brings huge trouble.
  • the present invention proposes an interface-modified sodium ion battery hard carbon negative electrode material/negative electrode, preparation Methods and Applications.
  • a technical solution disclosed by the invention an interface-modified hard carbon negative electrode material for sodium ion batteries.
  • the surface of the hard carbon material is coated with a metal-organic complex film composed of a metal center and organic molecules coordinated, with a thickness of 1nm-100nm, preferably 3nm-30nm.
  • the metal center includes any one or more of Cu, Ni, Co, Zn or Fe; the organic molecules include benzotriazole, 2-mercaptobenzothiazole, benzothiazole, 3-amino - Any one or more of 1,2,4-triazole, quinoline, pyrazole, pyrrole or phenothiazine organic molecules containing O/N/S atoms and conjugated large ⁇ bond structures; the said The structure of the hard carbon material is spherical or massive, and its average particle size is 1-20 ⁇ m.
  • the interface-modified sodium-ion battery hard carbon negative electrode is prepared by using the above-mentioned interface-modified sodium-ion battery hard carbon negative electrode material.
  • the preparation method of the interface-modified hard carbon negative electrode of sodium ion battery has the following steps:
  • an interface-modified hard carbon negative electrode for sodium ion batteries The surface of the hard carbon negative electrode is coated with a metal-organic complex film composed of a metal center and organic molecules coordinated, with a thickness of 1nm-100nm, preferably 3nm-30nm.
  • the metal center includes any one or more of Cu, Ni, Co, Zn or Fe; the organic molecules include benzotriazole, 2-mercaptobenzothiazole, benzothiazole, 3-amino - Any one or more organic molecules containing O/N/S atoms and conjugated large ⁇ bond structures such as 1,2,4-triazole, quinoline, pyrazole, pyrrole or phenothiazine.
  • the preparation method of the interface-modified hard carbon negative electrode of sodium ion battery has the following steps:
  • the solvent of the organic molecule solution includes methanol, ethanol, water, dimethyl sulfoxide, N,N-dimethylformamide or acetonitrile. Any one or more of them; the concentration of organic molecules is 0.01-10g/L, the dissolution temperature is 10-80°C; the soaking time is 1min-2h.
  • the metal salts include any one or more of chloride, sulfate, fluoride or nitrate salts of Cu, Ni, Co, Zn or Fe metal ions.
  • the solvent of the metal salt solution includes any one or more of methanol, ethanol, water, dimethyl sulfoxide, N,N-dimethylformamide or acetonitrile; the concentration of metal ions is 0.01-10g/ L, dissolution temperature is 10-80°C; soaking time is 1min-2h.
  • the soaking and cleaning solvent includes any one or more of dimethyl sulfoxide, methanol, water, acetone, ethanol, acetonitrile or N,N-dimethylformamide; the soaking and cleaning time is 10s-1h; The drying method after soaking and cleaning is blast drying or vacuum drying, and the drying temperature is 20-100°C.
  • the invention also discloses a non-aqueous secondary battery, which includes a negative electrode plate, a positive electrode plate, a non-aqueous electrolyte, a separator and a casing, wherein the negative electrode plate adopts the above-mentioned interface-modified sodium ion battery hard carbon negative electrode As a negative pole piece.
  • the positive electrode sheet contains Na Na fast ion conductors such as sodium vanadium, pyrophosphates such as sodium iron pyrophosphate, fluorinated phosphates such as sodium vanadium fluorophosphate, sulfates such as sodium iron sulfate, etc.), Prussian blue compounds and other materials.
  • Na Na fast ion conductors such as sodium vanadium
  • pyrophosphates such as sodium iron pyrophosphate
  • fluorinated phosphates such as sodium vanadium fluorophosphate
  • sulfates such as sodium iron sulfate, etc.
  • Prussian blue compounds and other materials.
  • the ester electrolyte is obtained by dissolving sodium salt in an organic solvent with a concentration of 0.3-3mol/L.
  • the sodium salt includes sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate (NaClO 4 ), and trifluoromethyl Sodium sulfonate (NaSO 3 CF 3 ), sodium tetrafluoroborate (NaBF 4 ), sodium hexafluoroarsenate (NaAsF 6 ), sodium bis(fluorosulfonyl)imide (NaFSI), bis(trifluoromethanesulfonyl) ) sodium imide (NaTFSI); organic solvents include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl carbonate Ethyl ester (EMC), fluoroethylene carbonate (FEC), trimethyl phosphate (TMP), 1,3-dioxopent
  • the separators include polypropylene, polyethylene, non-woven separators, fiberglass or cellulose acetate separators, and coated separators based on the above materials.
  • the shell is made of organic plastic, aluminum shell, aluminum plastic film, stainless steel or their composite materials, and is in the shape of button, columnar or square.
  • the non-aqueous secondary battery is used in fields such as electric vehicles, wind power generation, solar power generation, smart grids or communication base stations.
  • the present invention uses a simple interface construction method to generate a layer of metal-organic complex film in situ on the surface of the electrode material.
  • the thickness of the film is 1nm-100nm.
  • the interface-modified sodium-ion battery hard carbon negative electrode prepared by the stable interface construction method of the present invention can well solve the existing problems of low cycle stability and rate performance of sodium-ion batteries, and the obtained sodium-ion battery has excellent cycle performance. stability.
  • the specific capacity of the sodium-ion battery prepared from the unmodified hard carbon negative electrode is 228mAh g -1 (0.05Ag -1 ).
  • the specific capacity retention rate is about 78.2% after 50 cycles.
  • the specific capacity is 0.1A g -1 Maintains 41.4% compared to 0.02A g -1 .
  • the sodium ion battery prepared by the present invention has both good rate performance and specific capacity (4%-40%), with a maximum specific capacity of 321.5mAh g -1 (0.05Ag -1 ), and a specific capacity retention rate after 50 cycles. At about 85.7%, the specific capacity at 0.1A g -1 remains 66.4% compared to 0.02A g -1 .
  • the rechargeable sodium-ion battery device prepared by the present invention has high cycle life and broad market application prospects.
  • Figure 1 is a scanning electron microscope image of the bulk (A) hard carbon material used in Example 1 and the spherical (B) hard carbon material in Example 6 of the present invention.
  • Figure 2 is a high-resolution transmission electron microscope image of the hard carbon anode interface-modified with 2-mercaptobenzothiazole and Cu ions prepared in Example 1 and the hard carbon anode without interface modification.
  • Figure 3 is a charge-discharge curve at 0.05A g -1 of the hard carbon negative electrode modified with 2-mercaptobenzothiazole and Cu ion interface prepared in Example 1 of the present invention and the pure hard carbon negative electrode.
  • Figure 4 is a graph showing the cycle performance of the hard carbon negative electrode prepared by using 2-mercaptobenzothiazole and Cu ion interface modification and the pure hard carbon negative electrode prepared in Example 1 of the present invention at 0.05 A g -1 .
  • Figure 5 is the infrared spectrum (A) and X-ray photoelectron spectrum (B) of the uninterface-modified hard carbon negative electrode and the interface-modified hard carbon negative electrode prepared in Example 2 of the present invention.
  • Figure 6 shows the charge-discharge curves of the interface-modified hard carbon negative electrode prepared in Example 2 of the present invention and the non-interface-modified hard carbon negative electrode at 0.05 A g - 1 .
  • Figure 7 is a graph showing the rate performance of the interface-modified hard carbon negative electrode prepared in Example 2 of the present invention and the non-interface-modified hard carbon negative electrode under different current densities.
  • Figure 8 is a high-resolution transmission electron microscope image of the SEI formed by the uninterface-modified hard carbon negative electrode (A) and the interface-modified hard carbon negative electrode (B) prepared in Example 2 of the present invention when discharged to 0.01V in the first cycle.
  • Figure 9 is a diagram of a soft-packed sodium-ion battery constructed in Embodiment 9 of the present invention.
  • the conductive agent and binder used in each embodiment of the present invention are conventional substances, wherein the conductive agent and binder are acetylene black and PVDF, and the mass ratio of the hard carbon negative electrode material to the conductive agent and binder is 8:1:1 .
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as the negative electrode material, which is mainly composed of micron block particles (as shown in Figure 1). Mix it with conductive agent and binder to form a slurry and coat it on copper foil. on and dry.
  • Preparation method of interface-modified hard carbon anode use methanol as the solvent, configure a 2-mercaptobenzothiazole (MBT) solution with a concentration of 0.05g/L, and use dimethyl sulfoxide as the solvent to configure a concentration of 0.05g/L CuCl solution; soak the uninterface-modified hard carbon negative electrode in the 2-mercaptobenzothiazole solution at 25°C for 5 minutes, take it out and dry it; further put it into the CuCl solution of the corresponding concentration, soak it at 25°C for 5 minutes, and use Wash with methyl sulfoxide and methanol solvents in sequence for 10 minutes, and dry to obtain the interface-modified hard carbon negative electrode for sodium ion batteries.
  • MTT 2-mercaptobenzothiazole
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte (1mol/L), use glass fiber separator and stainless steel battery shell, respectively.
  • the interface-modified hard carbon negative electrode and the interface-modified hard carbon negative electrode obtained in this example were assembled into a button-type sodium ion battery, and its electrochemical performance was tested.
  • Figure 2 is a high-resolution transmission electron microscope image of the hard carbon anode interface-modified with 2-mercaptobenzothiazole and Cu ions prepared in this example and without interface modification.
  • the thickness of the metal-organic complex film coated on the surface of the hard carbon anode is about Around 6nm.
  • Figure 3 shows the charge and discharge curves of the hard carbon anode interface-modified with 2-mercaptobenzothiazole and Cu ions prepared in this example and the hard carbon anode without interface modification at 0.05 A g -1 .
  • the specific capacity of the hard carbon negative electrode prepared in this example is 303mAh g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 32.9%.
  • Figure 4 is a cycle performance diagram of the hard carbon anode interface-modified with 2-mercaptobenzothiazole and Cu ions prepared in this example and the hard carbon anode without interface modification at 0.05A g -1 .
  • the unmodified hard carbon The specific capacity retention rate of the negative electrode after 50 cycles was 78.2%, and the specific capacity retention rate of the interface-modified hard carbon negative electrode after 50 cycles was 85.7%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a 2-mercaptobenzothiazole solution with a concentration of 0.1g/L.
  • the thickness of the metal-organic complex film is about 15nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, 1mol/L NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte, use glass fiber separator and stainless steel battery shell to assemble button-type sodium ions battery and test its electrochemical performance.
  • Figure 5 shows the infrared spectrum (A) and X-ray photoelectron spectrum (B) of the uninterface-modified hard carbon anode and the interface-modified hard carbon anode prepared in this example.
  • A infrared spectrum
  • B X-ray photoelectron spectrum
  • Figure 6 shows the charge and discharge curves of the interface-modified hard carbon negative electrode prepared in this embodiment and the non-interface-modified hard carbon negative electrode at 0.05 A g -1 .
  • the specific capacity of the hard carbon negative electrode prepared in this example is 310mAh g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 35.9%.
  • Figure 7 is a graph showing the rate performance of the interface-modified hard carbon negative electrode prepared in this embodiment and the non-interface-modified hard carbon negative electrode under different current densities. After being cycled 5 times at current densities of 0.02A g -1 , 0.05A g -1 and 0.1A g -1 respectively, the specific capacity retention rate of the hard carbon anode prepared in this example is about 66.4%, while the hard carbon negative electrode without interface modification has a specific capacity retention rate of about 66.4%. The specific capacity retention rate of the carbon negative electrode is about 41.4%. Compared with the hard carbon negative electrode without interface modification, the rate performance is improved by 60%, and the rate performance is significantly improved.
  • Figure 8 is a high-resolution transmission electron microscope image of the SEI formed by the non-interface-modified hard carbon negative electrode (A) and the interface-modified hard carbon negative electrode (B) prepared in this embodiment when discharged to 0.01V in the first cycle.
  • the SEI on the surface of the uninterface-modified hard carbon anode is rich in organic phase, which is easily dissolved in the electrolyte and has an unstable structure.
  • the interface-modified hard carbon negative electrode SEI has rich and clear lattice stripes, indicating that the SEI is mainly composed of inorganic substances, which has higher stability and can promote the structural stability of the electrode material.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a benzotriazole (BTA) solution with a concentration of 0.2g/L.
  • BTA benzotriazole
  • dimethyl sulfoxide as the solvent to prepare a solution with a concentration of 0.2g/L.
  • CuCl solution Soak the uninterface-modified hard carbon negative electrode in the benzotriazole solution at 30°C for 2 hours, take it out and dry it; further put it into the CuCl solution of the corresponding concentration, soak it at 30°C for 2 hours, and use dimethyl Wash with sulfoxide and methanol solvents in sequence for 5 minutes and dry to obtain an interface-modified hard carbon negative electrode for sodium ion batteries.
  • the thickness of the obtained metal-organic complex film is about 20nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, 1mol/L NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte, use glass fiber separator and stainless steel battery shell to assemble button-type sodium ions battery and test its electrochemical performance.
  • the specific capacity is 267mAh g -1 when the current density is 0.05A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 17.1%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a benzotriazole (BTA) solution with a concentration of 0.02g/L. In addition, use dimethyl sulfoxide as the solvent to prepare a solution with a concentration of 0.1g/L. CuCl solution; Soak the unmodified hard carbon negative electrode in the benzotriazole solution at 20°C for 1 hour, take it out and dry it; further put it into the CuCl solution of the corresponding concentration, soak it at 20°C for 1 hour, and use dimethyl Wash with sulfoxide and methanol solvents in sequence for 10 minutes and dry to obtain an interface-modified hard carbon negative electrode for sodium ion batteries. The thickness of the obtained metal-organic complex film is about 30nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte (1mol/L), use glass fiber separator and stainless steel battery shell to assemble into buckle sodium-ion battery to test its electrochemical performance.
  • the specific capacity is 238mAh g -1 at a current density of 0.05A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 4.4%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a 2-mercaptobenzothiazole (MBT) solution with a concentration of 0.1g/L. In addition, use dimethyl sulfoxide as the solvent to prepare a concentration of 0.1g/L. CuCl solution; add 2-mercaptobenzothiazole dropwise to the surface of the hard carbon electrode without interface modification, take it out and dry it; further add the CuCl solution dropwise to the obtained hard carbon negative electrode, wash it with methanol solvent for 10 minutes, and dry it. An interface-modified hard carbon negative electrode for sodium ion batteries was obtained, and the thickness of the metal-organic complex film obtained was about 25 nm.
  • MTT 2-mercaptobenzothiazole
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte (1mol/L), use glass fiber separator and stainless steel battery shell to assemble into buckle sodium-ion battery to test its electrochemical performance.
  • the specific capacity is 272mAh g -1 when the current density is 0.05A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 19.3%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Hard carbon negative electrode preparation method Use purchased commercial hard carbon as the negative electrode material, which is mainly composed of spherical particles (as shown in Figure 1). Mix it with conductive agent and binder to form a slurry and coat it on the copper foil. drying.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a benzotriazole (BTA) solution with a concentration of 0.2g/L.
  • BTA benzotriazole
  • dimethyl sulfoxide as the solvent to prepare a solution with a concentration of 0.2g/L.
  • CuCl solution soak the uninterface-modified hard carbon negative electrode in the benzotriazole solution at 35°C for 2 hours, take it out and dry it; further put it into a CuCl solution of corresponding concentration, soak it at 35°C for 2 hours, and wash with methanol solvent After drying for 20 minutes, the interface-modified hard carbon negative electrode for sodium ion batteries can be obtained.
  • the thickness of the obtained metal-organic complex film is about 25nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte (1mol/L), use cellulose acetate separator and stainless steel battery shell to assemble Button-type sodium-ion battery to test its electrochemical performance.
  • the specific capacity is 265mAh g -1 when the current density is 0.05A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 16.23%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a 2-mercaptobenzothiazole (MBT) solution with a concentration of 0.1g/L. In addition, use dimethyl sulfoxide as the solvent to prepare a concentration of 0.1g/L. CuCl solution; soak the uninterface-modified hard carbon negative electrode in the 2-mercaptobenzothiazole solution at 30°C for 30 minutes, take it out and dry it; further put it into the CuCl solution of the corresponding concentration, soak it at 30°C for 30 minutes, and rinse with methanol After washing with solvent for 20 minutes and drying, the interface-modified hard carbon negative electrode for sodium ion batteries can be obtained.
  • the thickness of the obtained metal-organic complex film is about 27nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaSO 3 CF 3 salt dissolved in DGM solvent as electrolyte (1mol/L), use glass fiber separator and stainless steel battery shell to assemble a button sodium ion battery, and test its Electrochemical properties.
  • the specific capacity is 282mAh g -1 when the current density is 0.2A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 23.68%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a 2-mercaptobenzothiazole (MBT) solution with a concentration of 0.1g/L.
  • MBT 2-mercaptobenzothiazole
  • dimethyl sulfoxide as the solvent to prepare a concentration of 0.1g/L.
  • CuCl solution soak the uninterface-modified hard carbon negative electrode in 2-mercaptobenzothiazole solution at 40°C for 2h, take it out and dry it; further soak it in 0.1g/L FeSO 4 solution, and soak it at 40°C for 2h. , wash with methanol solvent for 20 minutes, and dry to obtain an interface-modified hard carbon negative electrode for sodium ion batteries.
  • the thickness of the obtained metal-organic complex film is about 15nm.
  • Electrochemical performance test Use sodium metal sheet as counter electrode, NaPF 6 salt dissolved in EC:DEC solvent with a volume ratio of 1:1 as electrolyte (1mol/L), use glass fiber separator and stainless steel battery shell to assemble into buckle sodium-ion battery to test its electrochemical performance.
  • the specific capacity is 243mAh g -1 when the current density is 0.2A g -1 .
  • the specific capacity (228mAh g -1 ) is increased by 6.58%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Preparation method of hard carbon negative electrode Use purchased commercial hard carbon as negative electrode material, which is mainly composed of micron block particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon negative electrode use methanol as the solvent to prepare a 2-mercaptobenzothiazole solution with a concentration of 0.1g/L. In addition, use dimethyl sulfoxide as the solvent to prepare a CuCl solution with a concentration of 0.1g/L. ; Soak the uninterface-modified hard carbon negative electrode in 2-mercaptobenzothiazole solution at 50°C for 2 hours, take it out and dry it; further soak it in 0.1g/L FeSO 4 solution, soak it at 50°C for 2 hours, and use it with methanol After washing with solvent for 20 minutes and drying, the interface-modified hard carbon negative electrode for sodium ion batteries can be obtained. The thickness of the obtained metal-organic complex film is about 20nm.
  • Electrochemical performance test The positive electrode piece is obtained by coating it with NaNi 1/3 Fe 1/3 Mn 1/3 O 2 active material, conductive agent and binder.
  • NaPF 6 salt is dissolved in EC with a volume ratio of 1:1: DEC solvent is used as the electrolyte (1mol/L), glass fiber is used as the separator, the capacity ratio of the negative electrode and the positive electrode material is adjusted to 1:1.2, and the aluminum plastic film is used as the casing (as shown in Figure 9) to assemble a soft-packed sodium ion battery and test its electrochemical properties.
  • the specific capacity is 235mAh g -1 when the current density is 0.02A g -1 .
  • the specific capacity 210mAh g -1
  • the specific capacity is increased by 11.9%.
  • This embodiment is a preparation method and application of a hard carbon negative electrode prepared from interface-modified hard carbon powder. The steps are as follows:
  • Preparation method of interface-modified hard carbon powder Mix and disperse 0.5g of benzotriazole (BTA) and 0.25g of hard carbon powder (composed of micron lump particles) in 100 mL of methanol solution and continue stirring for 1 hour. It is centrifuged and dried; in addition, dissolve 1.277g of CuSO 4 in 150 mL of dimethyl sulfoxide, then add the hard carbon powder obtained in the previous step, stir vigorously for 2 minutes, centrifuge, wash three times, and dry to obtain the interface modification. Using hard carbon powder, the thickness of the metal-organic complex film obtained is about 20nm.
  • Electrochemical performance test Mix the interface-modified hard carbon powder, conductive agent, and binder in N,N-dimethylpyrrolidone solvent to prepare a slurry, apply it on copper foil, and dry it. A sodium metal sheet was used as the counter electrode, NaPF 6 salt was dissolved in EC:DEC solvent with a volume ratio of 1:1 as the electrolyte (1mol/L), and glass fiber was used as the separator to assemble a button sodium ion battery and test its electrochemistry. performance.
  • the specific capacity of the hard carbon anode prepared from the interface-modified hard carbon powder is 247mAh g -1 , which is higher than that of the hard carbon anode without interface modification.
  • the capacity (228mAh g -1 ) is increased by 8.33%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Hard carbon negative electrode preparation method Use purchased commercial hard carbon as the negative electrode material, which is mainly composed of spherical particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • the preparation method of the interface-modified hard carbon anode use ethanol as the solvent to prepare a benzothiazole (BT) solution with a concentration of 5g/L, and use acetonitrile as the solvent to prepare a ZnCl 2 solution with a concentration of 5g/L;
  • the modified hard carbon negative electrode was soaked in the benzothiazole solution at 80°C for 1 min, taken out and dried; further put it into a ZnCl 2 solution of corresponding concentration, soaked at 80°C for 1 min, and washed with ethanol and acetonitrile solvents for 10 s in sequence, at 20°C After drying, the interface-modified hard carbon negative electrode for sodium ion batteries can be obtained, and the thickness of the obtained metal-organic complex film is about 25nm.
  • Electrochemical performance test Use sodium iron phosphate as the positive electrode, 0.3mol/L NaBF 4 salt dissolved in EMC:DMC solvent with a volume ratio of 1:1 as the electrolyte, cellulose acetate separator as the separator, and stainless steel as the casing. Assemble a button sodium-ion battery and test its electrochemical performance. In the voltage range of 0.01-2.0V, the specific capacity is 237mAh g -1 when the current density is 0.05A g -1 . Compared with the hard carbon negative electrode without interface modification, the specific capacity (228mAh g -1 ) is increased by 4.0%.
  • This embodiment is a preparation method and application of an interface-modified hard carbon negative electrode for sodium ion batteries. The steps are as follows:
  • Hard carbon negative electrode preparation method Use purchased commercial hard carbon as the negative electrode material, which is mainly composed of spherical particles. Mix it with conductive agent and binder to form a slurry, apply it on copper foil, and dry it.
  • Preparation method of interface-modified hard carbon anode use water as the solvent, prepare a pyrazole (Pyro) solution with a concentration of 10g/L, and use N,N-dimethylformamide as the solvent to prepare a NiSO solution with a concentration of 10g/L 4 solution; soak the uninterface-modified hard carbon negative electrode in the pyrazole solution at 20°C for 2h, take it out and dry it; further put it into the NiSO 4 solution of the corresponding concentration, soak it at 10°C for 2h, and use N, N-dioxide
  • the interface-modified hard carbon negative electrode for sodium ion batteries can be obtained by washing with methylformamide and water solvent for 1 hour and drying at 70°C.
  • the thickness of the obtained metal-organic complex film is about 30nm.
  • Electrochemical performance test Use sodium fluorophosphate vanadium compound as the positive electrode, 1.0mol/L NaClO 4 salt dissolved in EC:PC solvent with a volume ratio of 1:1, 5% FEC as the additive electrolyte, and regulate the negative and positive electrodes.
  • the material capacity ratio is 1:1.2
  • polyvinylidene fluoride is used as the separator
  • a composite material of aluminum shell and aluminum-plastic film is used as the outer shell.
  • a button-type sodium-ion battery is assembled and its electrochemical performance is tested.
  • the specific capacity is 240mAh g -1 when the current density is 0.02A g -1 .
  • the specific capacity (220mAh g -1 ) is increased by 9.09%.

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Abstract

本发明属于钠离子电池领域，涉及硬碳负极，具体涉及一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用。在球状或块状商业化硬碳材料表面或由硬碳材料所制备的负极表面包覆一层金属有机配合物薄膜，该薄膜由金属中心和有机分子在碳材料表面通过配位聚合而成。方法为：将硬碳材料或由硬碳材料所制备的负极先后在有机分子溶液和金属离子溶液中浸泡、干燥后，即可得到界面修饰的硬碳材料制备的硬碳负极或界面修饰的硬碳负极。本发明创新性引入金属有机配合物薄膜，促进了界面离子电导率和稳定性，显著提升硬碳负极储钠比容量、倍率性能和循环稳定性，有效解决目前钠离子电池负极困境；同时制备方法简单，适合大规模操作，应用前景广阔。

Description

一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用 技术领域
本发明属于钠离子电池技术领域，涉及硬碳负极制备，具体涉及一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用。
背景技术
钠离子电池作为可再生能源和大规模储能系统之间能量传输的媒介，以其资源储量丰富、低成本等优点，被看作是最有前景的下一代储能系统之一。然而现有的钠离子电池技术却并不能满足当前社会对大规模储能电站和新能源电车等领域的需求。因此，发展具有低成本、高能量密度、高功率密度和长循环寿命的钠离子电池成为目前的迫切需求。
硬碳由于低的储钠电压(约为0.1V)和高储量而被广泛研究，并应用于钠离子电池负极材料上，并成为钠离子电池商业化中的主要候选负极材料。然而，大多数可以规模化生产的硬碳均表现出低的比容量和差的倍率性能，钠离子电池在其具有价格优势的同时却未表现出高的电化学性能，这对硬碳材料的应用带来了巨大的困扰。
研究表明，在硬碳材料表面形成固态电解质界面(SEI)将有助于提高硬碳材料的稳定性和离子电导率等性质，并将有助于提高其储钠性能。如在硬碳材料表面包覆一层Al 2O 3或者NaPO 3等，从而有效减小材料与电解液在充放电过程中的副反应。然而，该制备方法存在制备时间长、加工成本高的问题。又如，在电解液中加入添加剂使其在电极材料表面分解优化SEI。然而，分布在电解液中的添加剂利用效率低，且容易影响电解液自身性质。
因此，为了实现钠离子电池的进一步产业化突破，迫切需要一种便宜且高效的电极材料/电解液界面稳定的方法。
发明内容
针对现有技术中存在钠离子电池硬碳负极制备时间长、成本高以及钠离子电池电解液界面不稳定的技术问题，本发明提出一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用。通过在硬碳负极材料表面或由硬碳材料所制备的负极表面诱导形成稳定均匀的SEI，提升其比容量和倍率性能，制备方法简单，适合大规模操作，具有广阔的应用前景。
为了达到上述目的，本发明的技术方案是这样实现的：
本发明公开的一种技术方案：一种界面修饰的钠离子电池硬碳负极材料，在硬碳材料表面包覆一层由金属中心和有机分子配位而成的金属有机配合物薄膜，厚度为1nm-100nm，优 选为3nm-30nm。
所述的金属中心包括Cu、Ni、Co、Zn或Fe中的任意一种或几种；所述的有机分子包括苯并三氮唑、2-巯基苯并噻唑、苯并噻唑、3-氨基-1，2，4-三唑、喹啉、吡唑、吡咯或吩噻嗪类含有O/N/S原子和共轭大π键结构的有机分子中的任意一种或几种；所述的硬碳材料的结构为球状或块状，其平均粒径为1-20μm。
利用上述的界面修饰的钠离子电池硬碳负极材料制备得到的界面修饰的钠离子电池硬碳负极。
所述的界面修饰的钠离子电池硬碳负极的制备方法，步骤如下：
(1)将硬碳材料的粉末浸泡于有机分子溶液中或将有机分子溶液滴加到未界面修饰的硬碳材料上，使硬碳材料被有机分子包覆后干燥，得到硬碳材料a1；
(2)然后将硬碳材料a1浸泡于金属盐溶液中或将金属盐溶液滴加到硬碳材料a1上，得到硬碳材料b1，将硬碳材料b1在溶剂中浸泡清洗，浸泡清洗完成后干燥，得到界面修饰的钠离子电池硬碳负极材料；
(3)将界面修饰的钠离子电池硬碳负极材料、导电剂和粘结剂混合于溶剂中调制浆料，涂布在铜箔上，烘干得到界面修饰的钠离子电池硬碳负极。
本发明公开的另一种技术方案：一种界面修饰的钠离子电池硬碳负极，在硬碳负极表面包覆一层由金属中心和有机分子配位而成的金属有机配合物薄膜，厚度为1nm-100nm，优选为3nm-30nm。
所述的金属中心包括Cu、Ni、Co、Zn或Fe中的任意一种或几种；所述的有机分子包括苯并三氮唑、2-巯基苯并噻唑、苯并噻唑、3-氨基-1，2，4-三唑、喹啉、吡唑、吡咯或吩噻嗪等含有O/N/S原子和共轭大π键结构的有机分子中的任意一种或几种。
所述的界面修饰的钠离子电池硬碳负极的制备方法，步骤如下：
(1)将硬碳负极浸泡于有机分子溶液中或将有机分子溶液滴加到硬碳负极上，使硬碳负极被有机分子包覆后干燥，得到硬碳负极a2；
(2)然后将硬碳负极a2浸泡于金属盐溶液中或将金属盐溶液滴加到硬碳负极a2上，得到硬碳负极b2，将硬碳负极b2在溶剂中浸泡清洗，浸泡清洗完成后干燥，即得到界面修饰的钠离子电池硬碳负极。
在本发明的界面修饰的钠离子电池硬碳负极的制备方法中，所述的有机分子溶液的溶剂包括甲醇、乙醇、水、二甲基亚砜、N,N-二甲基甲酰胺或乙腈中的任意一种或多种；有机分子的浓度为0.01-10g/L，溶解温度为10-80℃；浸泡时间为1min-2h。
所述的金属盐包括Cu、Ni、Co、Zn或Fe金属离子的氯化物、硫酸物、氟化物或硝酸物盐中的任意一种或多种。
所述的金属盐溶液的溶剂包括甲醇、乙醇、水、二甲基亚砜、N,N-二甲基甲酰胺或乙腈中的任意一种或多种；金属离子的浓度为0.01-10g/L，溶解温度为10-80℃；浸泡时间为1min-2h。
所述的浸泡清洗溶剂包括二甲基亚砜、甲醇、水、丙酮、乙醇、乙腈或N,N-二甲基甲酰胺中的任意一种或几种；浸泡清洗的时间为10s-1h；浸泡清洗完成后的干燥方法为鼓风干燥或真空干燥，干燥温度为20-100℃。
本发明还公开了一种非水二次电池，包括负极极片、正极极片、非水电解液、隔膜和外壳，其中所述的负极极片采用上述的界面修饰的钠离子电池硬碳负极作为负极极片。
所述的正极极片：包含Na xMO 2层状化合物(M包括Fe、Mn、Cu、Cr、Ni中的任意一种或多种)、聚阴离子型化合物(磷酸铁钠等磷酸盐、磷酸钒钠等Na快离子导体、焦磷酸铁钠等焦磷酸盐、氟磷酸钒钠等氟化磷酸盐、硫酸铁钠等硫酸盐等)、普鲁士蓝类化合物等材料。
所述的酯类电解液为钠盐溶于有机溶剂中得到，浓度为0.3-3mol/L，钠盐包括六氟磷酸钠(NaPF 6)、高氯酸钠(NaClO 4)、三氟甲基磺酸钠(NaSO 3CF 3)、四氟硼酸钠(NaBF 4)、六氟砷酸钠(NaAsF 6)、双(氟磺酰)亚胺钠(NaFSI)、双(三氟甲基磺酰)亚胺钠(NaTFSI)的任意一种或几种；有机溶剂包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、氟代碳酸乙烯酯(FEC)、磷酸三甲酯(TMP)、1,3-二氧环戊烷(DOL)、四氢呋喃(THF)、乙二醇二甲醚(DME)、氟代碳酸乙烯酯(FEC)、二乙二醇二甲醚(DGM)、三乙二醇二甲醚(TGM)中的任意一种或几种。
所述的隔膜包括聚丙烯、聚乙烯、无纺布隔膜、玻璃纤维或醋酸纤维素隔膜以及以上述材料为基底的涂覆隔膜。
所述的外壳包括采用有机塑料、铝壳、铝塑膜、不锈钢或它们的复合材料，形状为扣式、柱状或方形。
所述的非水二次电池应用在电动车、风力发电、太阳能发电、智能电网或通信基站等领域。
本发明具有以下有益效果：
1、针对硬碳负极在循环过程中电解液会在硬碳表面形成不稳定的SEI膜的问题，本发 明通过一种简单的界面构筑方法在电极材料表面原位生成一层金属有机配合物薄膜，薄膜的厚度为1nm-100nm。将该电极材料组装为钠离子电池后，电极材料表面引入的金属有机聚合物薄膜能够与SEI膜结合，促进SEI膜的稳定性，最终使电解液在电极材料表面分解形成一层均匀、超薄、无机盐为主体的SEI保护膜。该SEI保护膜能够缓冲电极材料体积膨胀和降低活性材料溶解现象，阻止酯类电解液的过度分解。
2、本发明利用稳定界面构筑方法制备的界面修饰的钠离子电池硬碳负极可以很好地解决现有的钠离子电池循环稳定性和倍率性能低的问题，获得的钠离子电池具有优异的循环稳定性。未经修饰的硬碳负极制备的钠离子电池的比容量为228mAh g -1(0.05Ag -1)，在经过50次循环后比容量保持率为78.2％左右，在0.1A g -1比容量相比0.02A g -1保持41.4％。而本发明制备的钠离子电池同时具有良好的倍率性能和比容量(4％-40％)，比容量最高为321.5mAh g -1(0.05Ag -1)，50次循环后的比容量保持率为85.7％左右，在0.1A g -1比容量相比0.02A g -1保持66.4％。
3、本发明制备的可充放钠离子电池器件具有高循环寿命，具有广阔的市场应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述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发明的一些实施例，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附图。
图1为本发明实施例1所用的块状(A)和实施例6中球状(B)硬碳材料扫描电镜图。
图2是本实施例1制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和未界面修饰硬碳负极高分辨透射电镜图
图3为本发明实施例1制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和纯硬碳负极在0.05A g -1下的充放电曲线图。
图4为本发明实施例1制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和纯硬碳负极在0.05A g -1下的循环性能图。
图5是本发明实施例2制备的未界面修饰的硬碳负极和界面修饰的硬碳负极的红外光谱(A)和X射线光电子能谱图(B)。
图6为本发明实施例2制备的界面修饰的硬碳负极和未界面修饰的硬碳负极在0.05A g - 1下的充放电曲线。
图7为本发明实施例2制备的界面修饰的硬碳负极和未界面修饰的硬碳负极在不同电流密度下的倍率性能图。
图8为本发明实施例2制备的未界面修饰的硬碳负极(A)和界面修饰的硬碳负极(B)在首周放电至0.01V形成的SEI的高分辨透射电镜图。
图9为本发明实施例9构筑的软包钠离子电池图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明各实施例所用导电剂和粘结剂均为常规物质，其中导电剂和粘结剂为乙炔黑和PVDF，硬碳负极材料与导电剂和粘结剂的质量比为8:1:1。
实施例1
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成(如图1所示)，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.05g/L的2-巯基苯并噻唑(MBT)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.05g/L的CuCl溶液；将未界面修饰的硬碳负极在25℃下浸泡在2-巯基苯并噻唑溶液5min，取出干燥；进一步将其放入相应浓度的CuCl溶液中，25℃下浸泡5min，用二甲基亚砜和甲醇溶剂依次洗涤10min，烘干即可得到界面修饰的钠离子电池硬碳负极。
电化学性能测试：用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，利用玻璃纤维隔膜和不锈钢电池壳，分别以未界面修饰的硬碳负极和本实施例得到的界面修饰的硬碳负极组装成扣式钠离子电池，测试其电化学性能。
图2是本实施例制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和未界面修饰的高分辨透射电镜图，硬碳负极表面包覆的金属有机配合物薄膜厚度约为6nm左右。
图3为本实施例制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和未界面修饰的硬碳负极在0.05A g -1下的充放电曲线。在0.01-2.0V电压范围内，电流密度为0.05A g -1时本实施例制备的硬碳负极比容量为303mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升32.9％。
图4为本实施例制备的利用2-巯基苯并噻唑和Cu离子界面修饰的硬碳负极和未界面修饰的硬碳负极在0.05A g -1下的循环性能图，未经修饰的硬碳负极循环50次比容量保持率为78.2％，界面修饰的硬碳负极循环50次比容量保持率为85.7％。
实施例2
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.1g/L的2-巯基苯并噻唑溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将未界面修饰的硬碳负极在30℃下浸泡在2-巯基苯并噻唑溶液1.5h，取出干燥；进一步将其放入相应浓度的CuCl溶液中，30℃下浸泡1.5h，用二甲基亚砜和甲醇溶剂依次洗涤5min，烘干即可得到界面修饰的钠离子电池硬碳负极，其金属有机配合物薄膜厚度约为15nm左右。
电化学性能测试：用钠金属片作为对电极，1mol/LNaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。图5为本实施例制备的未界面修饰的硬碳负极和界面修饰的硬碳负极的红外光谱(A)和X射线光电子能谱图(B)。其中，相比于未界面修饰的硬碳负极，界面修饰后的硬碳负极中存在C-N键和Cu-N/Cu-S化学键，证明了界面金属有机配位结构的形成。
图6为本实施例制备的界面修饰的硬碳负极和未界面修饰的硬碳负极在0.05A g -1下的充放电曲线。在0.01-2.0V电压范围内，电流密度为0.05A g -1时本实施例制备的硬碳负极比容量为310mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升35.9％。
图7为本实施例制备的界面修饰的硬碳负极和未界面修饰的硬碳负极在不同电流密度下的倍率性能图。在0.02A g -1、0.05A g -1和0.1A g -1的电流密度下分别循环5次，本实施例制备的硬碳负极比容量保持率在66.4％左右，而未界面修饰的硬碳负极比容量保持率为41.4％左右，相比于未界面修饰的硬碳负极倍率性能提升了60％，在倍率性能有明显提升。
图8为本实施例制备的未界面修饰的硬碳负极(A)和界面修饰的硬碳负极(B)在首周放电至0.01V形成的SEI的高分辨透射电镜图。未界面修饰的硬碳负极表面SEI是富有机相，易溶解在电解液中同时结构不稳定。而界面修饰的硬碳负极SEI具有丰富的和清晰的晶格条纹，说明该SEI主要由无机物组成，其具有更高的稳定性，能够促进电极材料的结构稳定性。
实施例3
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.2g/L的苯并三氮唑(BTA)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.2g/L的CuCl溶液；将未界面修饰的硬碳负极在30℃下浸泡在苯并三氮唑溶液2h，取出干燥；进一步将其放入相应浓度的CuCl溶液中，30℃下浸泡2h，用二甲基亚砜和甲醇溶剂依次洗涤5min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为20nm左右。
电化学性能测试：用钠金属片作为对电极，1mol/LNaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05A g -1时比容量为267mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升17.1％。
实施例4
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.02g/L的苯并三氮唑(BTA)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将未界面修饰的硬碳负极在20℃下浸泡在苯并三氮唑溶液1h，取出干燥；进一步将其放入相应浓度的CuCl溶液中，20℃下浸泡1h，用二甲基亚砜和甲醇溶剂依次洗涤10min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为30nm左右。
电化学性能测试：用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05A g -1时比容量为238mAh g - 1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升4.4％。
实施例5
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.1g/L的2-巯基苯并噻唑 (MBT)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将2-巯基苯并噻唑滴加至未界面修饰的硬碳极表面，取出干燥；进一步将CuCl溶液滴加至获得的硬碳负极上，用甲醇溶剂洗涤10min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为25nm左右。
电化学性能测试：用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05A g -1时比容量为272mAh g - 1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升19.3％。
实施例6
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由球状颗粒(如图1所示)组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.2g/L的苯并三氮唑(BTA)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.2g/L的CuCl溶液；将未界面修饰的硬碳负极在35℃下浸泡在苯并三氮唑溶液2h，取出干燥；进一步将其放入相应浓度的CuCl溶液中，35℃下浸泡2h，用甲醇溶剂洗涤20min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为25nm左右。
电化学性能测试：用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，利用醋酸纤维素隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05A g -1时比容量为265mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升16.23％。
实施例7
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.1g/L的2-巯基苯并噻唑(MBT)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将未界面修饰的硬碳负极在30℃下浸泡在2-巯基苯并噻唑溶液30min，取出干燥；进一步将其放入相应浓度的CuCl溶液中，30℃下浸泡30min，用甲醇溶剂洗涤20min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为27nm左右。
电化学性能测试：用钠金属片作为对电极，NaSO 3CF 3盐溶解在DGM溶剂作为电解液(1mol/L)，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.2A g -1时比容量为282mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升23.68％。
实施例8
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.1g/L的2-巯基苯并噻唑(MBT)溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将未界面修饰的硬碳负极在40℃下浸泡在2-巯基苯并噻唑溶液2h，取出干燥；进一步将其浸泡于0.1g/L的FeSO 4溶液中，40℃下浸泡2h，用甲醇溶剂洗涤20min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为15nm左右。
电化学性能测试：用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，利用玻璃纤维隔膜和不锈钢电池壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.2A g -1时比容量为243mAh g - 1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升6.58％。
实施例9
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由微米块状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以甲醇为溶剂，配置浓度为0.1g/L的2-巯基苯并噻唑溶液，另外，以二甲基亚砜为溶剂配置浓度为0.1g/L的CuCl溶液；将未界面修饰的硬碳负极在50℃下浸泡在2-巯基苯并噻唑溶液2h，取出干燥；进一步将其浸泡于0.1g/L的FeSO 4溶液中，50℃下浸泡2h，用甲醇溶剂洗涤20min，烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为20nm左右。
电化学性能测试：用NaNi 1/3Fe 1/3Mn 1/3O 2活性材料、导电剂和粘结剂涂布获得正极极片，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，玻璃纤维作为隔膜，调控负极和正极材料容量比例为1:1.2，以铝塑膜为外壳(如图9所示)组装成软包钠离子电池，测试其电化学性能。在1.0-3.5V电压范围内，电流密度为0.02A g -1时比容 量为235mAh g -1。其相比于未界面修饰的硬碳负极比容量(210mAh g -1)提升11.9％。
实施例10
本实施例为由界面修饰的硬碳粉末所制备的硬碳负极的制备方法和其应用，步骤如下：
界面修饰的硬碳粉末制备方法：将0.5g的苯并三氮唑(BTA)和0.25g的硬碳粉末(由微米块状颗粒组成)混合分散在100mL甲醇溶液中持续搅拌1h，将其离心干燥；另外，将1.277g的CuSO 4溶解于150mL的二甲基亚砜中，然后加入上一步获得的硬碳粉末，剧烈搅拌2min，离心、洗涤三次、烘干即可得到界面修饰的硬碳粉末，获得的金属有机配合物薄膜厚度约为20nm左右。
电化学性能测试：将界面修饰的硬碳粉末和导电剂和粘结剂混合于N,N-二甲基吡咯烷酮溶剂中调制浆料，涂布在铜箔上，烘干。用钠金属片作为对电极，NaPF 6盐溶解在体积比为1:1的EC：DEC溶剂作为电解液(1mol/L)，玻璃纤维作为隔膜，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05Ag -1时，界面修饰的硬碳粉末制备的硬碳负极比容量为247mAh g -1，其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升8.33％。
实施例11
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由球状颗粒组成，将其和导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以乙醇为溶剂，配置浓度为5g/L的苯并噻唑(BT)溶液，另外，以乙腈为溶剂，配置浓度为5g/L的ZnCl 2溶液；将未界面修饰的硬碳负极在80℃下浸泡在苯并噻唑溶液1min，取出干燥；进一步将其放入相应浓度的ZnCl 2溶液中，80℃下浸泡1min，用乙醇和乙腈溶剂依次洗涤10s，20℃烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为25nm左右。
电化学性能测试：用磷酸铁钠作为正极极片，0.3mol/L NaBF 4盐溶解在体积比为1:1的EMC：DMC溶剂作为电解液，醋酸纤维素隔膜作为隔膜，以不锈钢作为外壳，组装成扣式钠离子电池，测试其电化学性能。在0.01-2.0V电压范围内，电流密度为0.05A g -1时比容量为237mAh g -1。其相比于未界面修饰的硬碳负极比容量(228mAh g -1)提升4.0％。
实施例12
本实施例为界面修饰的钠离子电池硬碳负极的制备方法和应用，步骤如下：
硬碳负极制备方法：将购买的商业化硬碳作为负极材料，主要由球状颗粒组成，将其和 导电剂、粘结剂混合成浆料涂布在铜箔上，烘干。
界面修饰的硬碳负极制备方法：以水为溶剂，配置浓度为10g/L的吡唑(Pyro)溶液，另外，以N,N-二甲基甲酰胺为溶剂配置浓度为10g/L的NiSO 4溶液；将未界面修饰的硬碳负极在20℃下浸泡在吡唑溶液2h，取出干燥；进一步将其放入相应浓度的NiSO 4溶液中，10℃下浸泡2h，用N,N-二甲基甲酰胺和水溶剂依次洗涤1h，70℃烘干即可得到界面修饰的钠离子电池硬碳负极，获得的金属有机配合物薄膜厚度约为30nm左右。
电化学性能测试：用氟磷酸钒钠化合物作为正极极片，1.0mol/L NaClO 4盐溶解在体积比为1:1的EC：PC溶剂，5％FEC作为添加剂的电解液，调控负极和正极材料容量比例为1:1.2，聚偏氟乙烯作为隔膜，以铝壳和铝塑膜的复合材料作为外壳，组装成扣式钠离子电池，测试其电化学性能。在1.0-4.0V电压范围内，电流密度为0.02A g -1时比容量为240mAh g -1。其相比于未界面修饰的硬碳负极比容量(220mAh g -1)提升9.09％。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (14)

  1. 一种界面修饰的钠离子电池硬碳负极材料，其特征在于：在硬碳材料表面包覆一层由金属中心和有机分子配位而成的金属有机配合物薄膜，厚度为1nm-100nm。
  2. 根据权利要求1所述的界面修饰的钠离子电池硬碳负极材料，其特征在于：所述的金属中心包括Cu、Ni、Co、Zn或Fe中的任意一种或几种；所述的有机分子包括苯并三氮唑、2-巯基苯并噻唑、苯并噻唑、3-氨基-1，2，4-三唑、喹啉、吡唑、吡咯或吩噻嗪类含有O/N/S原子和共轭大π键结构的有机分子中的任意一种或几种。
  3. 根据权利要求1所述的界面修饰的钠离子电池硬碳负极材料，其特征在于：所述金属有机配合物薄膜厚度为3nm-30nm。
  4. 一种界面修饰的钠离子电池硬碳负极，其特征在于：利用权利要求1-3任意一项所述的界面修饰的钠离子电池硬碳负极材料制备得到。
  5. 一种界面修饰的钠离子电池硬碳负极，其特征在于：在硬碳负极表面包覆一层由金属中心和有机分子配位而成的金属有机配合物薄膜，厚度为1nm-100nm。
  6. 根据权利要求4所述的界面修饰的钠离子电池硬碳负极，其特征在于：所述的金属中心包括Cu、Ni、Co、Zn或Fe中的任意一种或几种；所述的有机分子包括苯并三氮唑、2-巯基苯并噻唑、苯并噻唑、3-氨基-1，2，4-三唑、喹啉、吡唑、吡咯或吩噻嗪类含有O/N/S原子和共轭大π键结构的有机分子中的任意一种或几种。
  7. 根据权利要求4所述的界面修饰的钠离子电池硬碳负极，其特征在于：所述金属有机配合物薄膜厚度为3nm-30nm。
  8. 权利要求4所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于，步骤如下：
    (1)将硬碳材料的粉末浸泡于有机分子溶液中或将有机分子溶液滴加到未界面修饰的硬碳材料上，使硬碳材料被有机分子包覆后干燥，得到硬碳材料a1；
    (2)然后将硬碳材料a1浸泡于金属盐溶液中或将金属盐溶液滴加到硬碳材料a1上，得到硬碳材料b1，将硬碳材料b1在溶剂中浸泡清洗，浸泡清洗完成后干燥，得到界面修饰的钠离子电池硬碳负极材料；
    (3)将界面修饰的钠离子电池硬碳负极材料、导电剂和粘结剂混合于溶剂中调制浆料，涂布在铜箔上，烘干得到界面修饰的钠离子电池硬碳负极。
  9. 权利要求5所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于，步骤如下：
    (1)将硬碳负极浸泡于有机分子溶液中或将有机分子溶液滴加到硬碳负极上，使硬碳负极 被有机分子包覆后干燥，得到硬碳负极a2；
    (2)然后将硬碳负极a2浸泡于金属盐溶液中或将金属盐溶液滴加到硬碳负极a2上，得到硬碳负极b2，将硬碳负极b2在溶剂中浸泡清洗，浸泡清洗完成后干燥，即得到界面修饰的钠离子电池硬碳负极。
  10. 根据权利要求8或9所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于：所述的有机分子溶液的溶剂包括甲醇、乙醇、水、二甲基亚砜、N,N-二甲基甲酰胺或乙腈中的任意一种或多种；有机分子的浓度为0.01-10g/L，浸泡温度为10-80℃；浸泡时间为1min-2h。
  11. 根据权利要求8或9所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于：所述的金属盐包括Cu、Ni、Co、Zn或Fe金属离子的氯化物、硫酸物、氟化物或硝酸物盐中的任意一种或多种，金属盐浓度为0.01-10g/L。
  12. 根据权利要求8或9所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于：所述的金属盐溶液的溶剂包括甲醇、乙醇、水、二甲基亚砜、N,N-二甲基甲酰胺或乙腈中的任意一种或多种；金属盐的浓度为0.01-10g/L，浸泡温度为10-80℃；浸泡时间为1min-2h。
  13. 根据权利要求8或9所述的界面修饰的钠离子电池硬碳负极的制备方法，其特征在于：所述的浸泡清洗溶剂包括二甲基亚砜、甲醇、水、丙酮、乙醇、乙腈或N,N-二甲基甲酰胺中的任意一种或几种；浸泡清洗的时间为10s-1h；浸泡清洗完成后的干燥方法为鼓风干燥或真空干燥，干燥温度为20-100℃。
  14. 一种非水二次电池，包括负极极片、正极极片、非水电解液、隔膜和外壳，其特征在于：所述的负极极片采用权利要求4或5所述的界面修饰的钠离子电池硬碳负极作为负极极片。
PCT/CN2022/131834 2022-06-23 2022-11-15 一种界面修饰的钠离子电池硬碳负极材料/负极、制备方法和应用 WO2023245967A1 (zh)

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