WO2023082505A1 - 原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途 - Google Patents

原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途 Download PDF

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WO2023082505A1
WO2023082505A1 PCT/CN2022/079725 CN2022079725W WO2023082505A1 WO 2023082505 A1 WO2023082505 A1 WO 2023082505A1 CN 2022079725 W CN2022079725 W CN 2022079725W WO 2023082505 A1 WO2023082505 A1 WO 2023082505A1
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precursor
positive electrode
sodium
electrode material
group
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French (fr)
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胡勇胜
胡紫霖
牛耀申
杨佯
容晓晖
陆雅翔
陈立泉
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中国科学院物理研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/121—Borates of alkali metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H01M4/36—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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 relates to the field of material technology, in particular to an oxide composite positive electrode material coated with borate in situ, a preparation method and application.
  • the existing energy storage methods are divided into physical energy storage and chemical energy storage.
  • pumped storage is currently the most used and the largest energy storage.
  • pumped storage is limited by geographical location, and the construction period is long.
  • Other physical energy storage such as compressed air energy storage and flywheel energy storage have not yet been completed. scale.
  • Electrochemical energy storage refers to the storage or release of electricity through reversible chemical reactions. It has attracted widespread attention due to its high energy conversion efficiency and power density, long cycle life, short construction period, and low maintenance costs.
  • electrochemical energy storage mainly includes high-temperature sodium-sulfur batteries, flow batteries, lead-acid batteries, and lithium-ion batteries.
  • Sodium-sulfur battery The working temperature of Na-S battery is 300°C. Metal sodium and elemental sulfur are in a molten state. If the material is damaged at high temperature, it will easily cause fire in the battery module. Therefore, the safety problem is very serious and it has not been applied on a large scale.
  • Flow batteries have low energy density and large volume. Compared with Ni-Cd batteries, lead-acid batteries have no memory effect and low cost. At present, they have always accounted for the vast majority of the energy storage market and are widely used.
  • lithium-ion batteries as electrochemical energy storage have been widely used in daily life due to their high energy density, high cycle stability, long cycle life, small size, light weight, and no pollution.
  • sodium and lithium belong to alkali metal elements in the periodic table of elements, they have similar physical and chemical properties.
  • Sodium-ion batteries and lithium-ion batteries have similar charging and discharging storage mechanisms. More importantly, sodium is abundant and widely distributed in nature, and it also has a significant price advantage.
  • aluminum foil can be used for the positive and negative current collectors of sodium-ion batteries, while copper can only be used for the negative electrodes of lithium-ion batteries. Obviously, copper is much more expensive than aluminum, so raw materials are cheap and easy to obtain.
  • Na x MO 2 M stands for 3d transition Among the metal elements, one or more may be included, such as Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Nb, Ru, Mo, Zn, etc.
  • the basis of the battery is the oxidation-reduction reaction, and the essence of the reaction is the change of the valence, that is, the transfer and offset of electrons.
  • the half reaction of losing electrons is an oxidation reaction, and the valence of the positive electrode material increases; the half reaction of gaining electrons is a reduction reaction, and the valence of the positive electrode material decreases.
  • the layered oxide cathode materials for sodium ion batteries described above all have transition metal materials that can undergo redox reactions, and the variable valence transition metals in the initial state of the materials are in a lower valence state, but the transition metal ions cannot be completely changed. There are still many cases where the capacity cannot be fully utilized, and the insufficient air stability of these cathode materials leads to poor consistency.
  • the embodiment of the present invention provides an oxide composite positive electrode material with in-situ coating of borate, its preparation method and application.
  • the cathode material is an air-stable, high-capacity, and high-cycle-stability material, and its cladding layer has a special shape, which is needle-like after contacting with air.
  • the coating layer is smoothly attached to the surface of the material before it comes into contact with the air. After it comes into contact with the air, the shape of the coating layer changes into a needle shape, so that the residual alkali produced on the surface of the material due to contact with the air is greatly reduced, and it is stable in the air.
  • the conductivity of the material is significantly improved, the conductivity and sodium ion diffusion capacity of the material are higher, the charge transfer resistance is lower, the first charge and discharge efficiency is higher, and the cycle capacity is better, especially the cycle life is longer.
  • the embodiment of the present invention provides an oxide composite cathode material with in-situ coating of borate, the general chemical formula of the material is: ⁇ A x By O z -Na a Li b Nic Cu d Mn e M f O 2+ ⁇ ;
  • Li, Ni, Cu, Mn, and M jointly occupy the transition metal ion position in the crystal structure; wherein M is an element for doping and replacing the transition metal position, including group IIIA, main group IV, group VA or One or more of the non-metallic elements of Group VIA and one or more of the transition metal elements of the fourth period and the fifth period;
  • the space group of the layered oxide composite cathode material is P63/mmc or P63/mcm or
  • the corresponding structure is P2 phase or O3 phase;
  • the A x By O z is a needle-like structure coating layer formed in situ on the surface of Na a Li b Nic Cu d Mne M f O 2+ ⁇ , and is used to generate Na
  • the layered oxide precursor of a Li b Ni c Cu d Mn e M f O 2+ ⁇ is generated during sintering; where ⁇ is the mass fraction of the coating material precursor in the layered oxide precursor, 0.1wt% ⁇ 10wt%; A is Li and/or Na, 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 10, 0 ⁇ z ⁇ 15.
  • the coating material precursor is boron oxide or boric acid; the molten coating material precursor forms A x By O z with a part of the sodium salt and/or lithium salt in the layered oxide precursor.
  • the embodiment of the present invention provides a method for preparing the oxide composite positive electrode material with in-situ coating of borate described in the first aspect, the method is a solid-phase method, comprising:
  • the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor are mixed in proportion to form a positive electrode material precursor; wherein the coating material precursor It is boron oxide or boric acid; the layered oxide precursor includes: sodium carbonate with a stoichiometric amount of 100wt% to 110wt% of required sodium, lithium carbonate with a stoichiometric amount of required sodium of 100wt% to 110wt%, nickel, copper, Oxides of manganese, oxides or carbonates of the required stoichiometric M; said M is an element for doping and substituting the transition metal position, including non-metals of Group IIIA, Group IV, Group VA or Group VIA One or more of the elements and one or more of the transition metal elements of the fourth period and the fifth period;
  • the precursor powder is placed in a muffle furnace or a tube furnace, and heat-treated in an air or oxygen atmosphere at 600°C to 1000°C for 2 to 24 hours;
  • the powder obtained after the heat treatment is ground to obtain the oxide composite positive electrode material with the surface in-situ coated with borate.
  • the embodiment of the present invention provides a method for preparing the oxide composite cathode material with in-situ coating of borate described in the first aspect, the method is a spray drying method, comprising:
  • the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor are mixed in proportion to form a positive electrode material precursor; wherein the coating material precursor It is boron oxide or boric acid; the layered oxide precursor includes: sodium carbonate or sodium nitrate with a required sodium stoichiometric ratio of 100wt% to 110wt%, lithium carbonate or nitric acid with a required sodium stoichiometric ratio of 100wt% to 110wt% Sodium lithium, oxides or nitrates of nickel, copper, manganese, oxides or carbonates of the required stoichiometric M; said M is an element for doping and substituting the transition metal site, including group IIIA, IV main One or more of the non-metal elements of group, VA group or VIA group and one or more of the transition metal elements of the fourth period and the fifth period;
  • Precursor powder is obtained after spray drying the slurry
  • the precursor powder is placed in a muffle furnace or a tube furnace, and heat-treated in an air or oxygen atmosphere at 600°C to 1000°C for 2 to 24 hours;
  • the powder obtained after the heat treatment is ground to obtain the oxide composite positive electrode material with the surface in-situ coated with borate.
  • the embodiment of the present invention provides a method for preparing the oxide composite positive electrode material with in-situ coating of borate described in the first aspect, the method is a combustion method, comprising:
  • the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor are mixed in proportion to form a positive electrode material precursor; wherein the coating material precursor It is boron oxide or boric acid; the layered oxide precursor includes: sodium nitrate with a stoichiometric amount of 100wt% to 110wt% of required sodium, lithium nitrate with a stoichiometric amount of required sodium of 100wt% to 110wt%, nickel, copper, Nitrate of manganese, the nitrate of the required stoichiometric M; said M is an element for doping and substituting the transition metal position, including one of the non-metallic elements of Group IIIA, Group IV, Group VA or Group VIA one or more and one or more of transition metal elements of the fourth period and the fifth period;
  • the precursor powder is obtained after drying the slurry
  • the precursor powder is placed in a muffle furnace or a tube furnace, and heat-treated in an air or oxygen atmosphere at 600°C to 1000°C for 2 to 24 hours;
  • the powder obtained after the heat treatment is ground to obtain the oxide composite positive electrode material with the surface in-situ coated with borate.
  • the embodiment of the present invention provides a method for preparing the oxide composite cathode material with in-situ coating of borate described in the first aspect, the method is a sol-gel method, comprising:
  • the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor are mixed in proportion to form a positive electrode material precursor; wherein the coating material precursor It is boron oxide or boric acid; the layered oxide precursor includes: a sodium salt with a stoichiometric amount of 100wt% to 110wt% of required sodium, a lithium salt with a stoichiometric amount of required sodium of 100wt% to 110wt%, nickel, copper, Nitrate or sulfate of manganese, nitrate or sulfate of the required stoichiometric M; said M is an element for doping and substituting the transition metal position, including group IIIA, main group IV, group VA or group VIA One or more of the non-metal elements and one or more of the transition metal elements of the fourth period and the fifth period; the sodium salt includes: one of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate
  • the precursor gel is placed in a crucible, and pre-fired for 2 hours under an air atmosphere of 200°C to 500°C;
  • the precursor powder is placed in a muffle furnace or a tube furnace, and heat-treated in an air or oxygen atmosphere at 600°C to 1000°C for 2 to 24 hours;
  • the powder obtained after the heat treatment is ground to obtain the oxide composite positive electrode material with in-situ coating of borate on the surface.
  • the embodiment of the present invention provides a method for preparing the oxide composite cathode material with in-situ coating of borate described in the first aspect, the method is a co-precipitation method, comprising:
  • the required stoichiometric nitrates of nickel, copper, manganese, lithium and M are dissolved in water and mixed in proportion to form a precursor solution;
  • the M is an element for doping and replacing the transition metal position, including group IIIA, IV main One or more of the non-metal elements of group, VA group or VIA group and one or more of the transition metal elements of the fourth period and the fifth period;
  • the obtained precipitate is cleaned with deionized water, and after drying, the precipitate is mixed with sodium carbonate and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor according to the stoichiometric ratio Uniformly mixing the obtained precursor;
  • the layered oxide precursor includes the sodium carbonate and the nickel, copper, manganese, lithium, M nitrate;
  • the precursor is placed in a crucible or a porcelain boat, and heat-treated in an air or oxygen atmosphere at 600°C to 1000°C for 2 to 24 hours;
  • the powder obtained after the heat treatment is ground to obtain the oxide composite positive electrode material with the surface in-situ coated with borate.
  • the embodiment of the present invention provides a positive pole piece of a sodium ion secondary battery, the positive pole piece comprising:
  • an embodiment of the present invention provides a sodium-ion secondary battery with the positive pole piece described in the seventh aspect.
  • the embodiment of the present invention provides a use of a sodium ion secondary battery, and the sodium ion secondary battery is used for electric vehicles, solar power generation, wind power generation, smart grid peak regulation, distributed power station, backup power supply or communication Large-scale energy storage equipment for base stations.
  • the oxide composite positive electrode material with in-situ coated borate proposed by the present invention melts at a lower temperature through boron oxide or boric acid, and forms a chemical general formula with a part of the sodium salt and lithium salt in the precursor of the positive electrode material.
  • the lithium borate salt or sodium borate salt of xByOz evenly and completely wraps the lithium-containing layered oxide positive electrode. After A x By O z contacts with air, it transforms into a needle-like structure, which greatly reduces the residual alkali generated on the surface of the material due to contact with air, significantly improves the stability in the air, and the material has higher conductivity and sodium ion diffusion capacity.
  • the charge transfer resistance is lower, the first charge and discharge efficiency is higher, and the cycle capacity is higher, so that the lithium-containing oxide composite positive electrode material coated with borate in situ on the surface has the characteristics of air stability, high capacity, and high cycle stability.
  • This material can be placed in 45%RH-60%RH air for more than 48 hours and still maintain a stable structure.
  • Fig. 1 is the flow chart of the preparation method of the oxide composite positive electrode material whose surface is in-situ coated with borate by the solid-phase method provided by the embodiment of the present invention
  • Fig. 2 is the flow chart of the preparation method of the oxide composite positive electrode material whose surface is in-situ coated with borate by the spray drying method provided by the embodiment of the present invention
  • Fig. 3 is a flow chart of a preparation method for preparing an oxide composite positive electrode material coated with borate on the surface in situ by a combustion method provided by an embodiment of the present invention
  • Fig. 4 is a flow chart of a method for preparing an oxide composite positive electrode material coated with borate on the surface in situ by the sol-gel method provided by the embodiment of the present invention
  • Fig. 5 is a flow chart of a preparation method for preparing an oxide composite positive electrode material coated with borate on the surface in situ by the co-precipitation method provided by the embodiment of the present invention
  • Fig. 6 is the XRD spectrum of multiple oxide composite positive electrode materials with in-situ coating of borate on the surface provided by the embodiment of the present invention with different molar percentages of elements;
  • Fig. 7 is the SEM image of the Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 material used for this example synthesized by the solid phase method provided in Example 1 of the present invention;
  • Figure 8 is the SEM image of the 0.5wt% Li 3 BO 3 -Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 material synthesized by the solid phase method provided in Example 1 of the present invention;
  • Fig. 9 is a comparison chart of the charging and discharging curves of the sodium ion battery prepared by the above two materials provided in Example 1 of the present invention at 2.0-4.3V;
  • Fig. 10 is a comparison chart of cycle curves of sodium ion batteries prepared from the above two materials provided in Example 1 of the present invention.
  • Figure 11 is the XRD spectrum of the oxide composite positive electrode material with in-situ coating of borate on the surface provided by Example 1 of the present invention before and after being placed in air with a humidity of 55% for 48 hours;
  • Figure 12 shows the sodium ion battery prepared by the two materials before and after the oxide composite positive electrode material with in-situ coating of borate on the surface provided by Example 1 of the present invention was placed in air with a humidity of 55% for 48 hours at 2.0-4.3V Charge and discharge curve comparison chart.
  • the embodiment of the present invention proposes a layered lithium-containing oxide composite positive electrode material with in-situ coating of borate on the surface, air stability, high capacity, and high cycle stability.
  • the general chemical formula of the material is: ⁇ A x By O z -Na a Li b Ni c Cu d Mn e M f O 2+ ⁇ ; the space group of the layered oxide composite cathode material is P63/mmc or P63/mcm or The corresponding structure is P2 phase or O3 phase.
  • Li, Ni, Cu, Mn, and M jointly occupy the transition metal ion position in the crystal structure; where M is an element for doping and replacing the transition metal position, including group IIIA, main group IV, group VA or One or more of the non-metallic elements of Group VIA and one or more of the transition metal elements of the fourth period and the fifth period;
  • a x By O z is the coating layer formed in situ on the surface of Na a Li b Ni c Cu d Mne M f O 2+ ⁇ , which is used to generate Na a Li b Ni c Cu
  • the layered oxide precursor of d Mn e M f O 2+ ⁇ is generated during the sintering process; the precursor of the coating material is boron oxide or boric acid; the molten state of the coating material precursor and the layered oxide precursor A part of the sodium salt and/ or lithium salt forms AxByOz .
  • ⁇ is the mass fraction of the coating material precursor in the layered oxide precursor, 0.1wt% ⁇ 10wt%; A is Li and/or Na, 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 10, 0 ⁇ z ⁇ 15.
  • the cladding layer has a special shape, which is needle-like after contact with air. The cladding layer is smoothly attached to the surface of the material before it comes into contact with the air. Since the material will inevitably come into contact with the air during the process of making the pole piece, the morphology of the cladding layer changes into a needle shape, and the residual alkali on the surface of the material is greatly reduced. The stability in the air is significantly improved, the conductivity of the material, the diffusion capacity of sodium ions are higher, the charge transfer resistance is lower, the first charge and discharge efficiency is higher, the cycle capacity is better, especially the cycle life is longer.
  • the preparation method of the oxide composite positive electrode material with in-situ coating of borate on the surface of the present invention is compatible with various processes, which will be described one by one below.
  • the oxide composite positive electrode material with in-situ coating of borate on the surface can be prepared by solid phase method.
  • the main steps are shown in Figure 1, including:
  • Step 110 mixing the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor in proportion to form a positive electrode material precursor;
  • the precursor of the coating material is boron oxide or boric acid;
  • the layered oxide precursor includes: sodium carbonate with a stoichiometric amount of 100wt% to 110wt% of required sodium, and lithium carbonate with a stoichiometric amount of required sodium of 100wt% to 110wt%.
  • oxides of nickel, copper, manganese, oxides or carbonates of required stoichiometric M is an element for doping and substituting the transition metal site, including group IIIA, main group IV, group VA or group VIA One or more of the non-metallic elements and one or more of the transition metal elements of the fourth period and the fifth period;
  • Step 120 using a ball milling method to uniformly mix the positive electrode material precursor to obtain a precursor powder
  • Step 130 placing the precursor powder in a muffle furnace or a tube furnace, and heat-treating in an air or oxygen atmosphere at 600° C. to 1000° C. for 2 to 24 hours;
  • Step 140 grinding the powder obtained after heat treatment to obtain an oxide composite cathode material with in-situ coating of borate on the surface.
  • the oxide composite positive electrode material with in-situ coating of borate on the surface can be prepared by spray drying method.
  • the main steps are shown in Figure 2, including:
  • Step 210 mixing the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor in proportion to form a positive electrode material precursor;
  • the precursor of the coating material is boron oxide or boric acid;
  • the layered oxide precursor includes: sodium carbonate or sodium nitrate with a stoichiometric amount of 100wt% to 110wt% of required sodium, and a stoichiometric amount of required sodium of 100wt% to 110wt%.
  • M is an element for doping and substituting the transition metal position, including group IIIA and main group IV , one or more of the non-metallic elements of Group VA or VIA, and one or more of the transition metal elements of the fourth period and the fifth period;
  • Step 220 adding ethanol or water to the positive electrode material precursor and stirring evenly to form a slurry
  • Step 230 spray-drying the slurry to obtain a precursor powder
  • Step 240 placing the precursor powder in a muffle furnace or tube furnace, and heat-treating it in an air or oxygen atmosphere at 600°C-1000°C for 2-24 hours;
  • Step 250 grinding the powder obtained after the heat treatment to obtain an oxide composite positive electrode material with in-situ coating of borate on the surface.
  • the oxide composite positive electrode material with in-situ coating of borate on the surface can be prepared by combustion method.
  • the main steps are shown in Figure 3, including:
  • Step 310 mixing the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor in proportion to form a positive electrode material precursor;
  • the precursor of the coating material is boron oxide or boric acid;
  • the precursor of the layered oxide includes: sodium nitrate with a stoichiometric amount of 100wt% to 110wt% of sodium required, and lithium nitrate with a stoichiometric amount of required sodium of 100wt% to 110wt%.
  • M is an element for doping and substituting the transition metal position, including one or more of the non-metallic elements of Group IIIA, Group IV, Group VA or Group VIA and the fourth One or more of the transition metal elements of the period and the fifth period;
  • Step 320 stirring the cathode material precursor and acetylacetone evenly to form a slurry
  • Step 330 drying the slurry to obtain a precursor powder
  • drying is preferably carried out at 80°C.
  • Step 340 placing the precursor powder in a muffle furnace or a tube furnace, and heat-treating it in an air or oxygen atmosphere at 600° C. to 1000° C. for 2 to 24 hours;
  • Step 350 grinding the powder obtained after the heat treatment to obtain an oxide composite cathode material with in-situ coating of borate on the surface.
  • the oxide composite cathode material with in-situ coating of borate on the surface can be prepared by the sol-gel method.
  • the main steps are shown in Figure 4, including:
  • Step 410 mixing the layered oxide precursor and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor in proportion to form a positive electrode material precursor;
  • the precursor of the coating material is boron oxide or boric acid
  • the precursor of the layered oxide includes: a sodium salt with a required sodium stoichiometric amount of 100wt% to 110wt%, and a required sodium stoichiometric amount of 100wt% to 110wt% lithium salt , nickel, copper, manganese nitrate or sulfate
  • M is an element for doping and substituting the transition metal position, including one or more of the non-metallic elements of Group IIIA, Group IV, Group VA or Group VIA
  • sodium salts include: one or more of sodium acetate, sodium nitrate, sodium carbonate or sodium sulfate
  • lithium salts include: lithium acetate, One or more of lithium nitrate, lithium carbonate or lithium sulfate;
  • Step 420 stirring at 50°C to 100°C, adding an appropriate amount of chelating agent, and evaporating to dryness to form a precursor gel;
  • Step 430 placing the precursor gel in a crucible, and pre-burning it for 2 hours in an air atmosphere at 200°C to 500°C;
  • Step 440 placing the precursor powder in a muffle furnace or a tube furnace, and heat-treating in an air or oxygen atmosphere at 600° C. to 1000° C. for 2 to 24 hours;
  • Step 450 grinding the powder obtained after the heat treatment to obtain an oxide composite positive electrode material with in-situ coating of borate on the surface.
  • the oxide composite positive electrode material with in-situ coating of borate on the surface can be prepared by co-precipitation method.
  • the main steps are shown in Figure 5, including:
  • Step 510 dissolving the required stoichiometric nitrates of nickel, copper, manganese, lithium and M in water in proportion to form a precursor solution;
  • M is an element for doping and substituting the transition metal site, including one or more of the non-metallic elements of Group IIIA, Group IV, Group VA or Group VIA, and transition metals of the fourth period and the fifth period. one or more of the elements;
  • Step 520 using a peristaltic pump to drop the precursor solution into the ammonia solution to generate a precipitate
  • step 530 the obtained precipitate is cleaned with deionized water, and after drying, the precipitate, sodium carbonate, and the coating material precursor accounting for 0.1wt% to 10wt% of the total mass of the layered oxide precursor are stoichiometrically than the precursor obtained by uniform mixing;
  • the layered oxide precursor includes sodium carbonate and nickel, copper, manganese, lithium, M nitrate;
  • Step 540 placing the precursor in a crucible or a porcelain boat, and heat-treating in an air or oxygen atmosphere at 600° C. to 1000° C. for 2 to 24 hours;
  • step 550 the powder obtained after the heat treatment is ground to obtain an oxide composite positive electrode material with in-situ coating of borate on the surface.
  • the above preparation methods can be used to prepare the layered lithium-containing oxide composite positive electrode material with in-situ coating of borate on the surface in the above embodiments.
  • the method provided in this embodiment is simple and easy, and the contained elements sodium, lithium, nickel, copper and manganese are all non-toxic and safe elements, which are abundant in the earth's crust, so the manufacturing cost is low and the materials used are safe and non-toxic. Suitable for mass-manufacturing applications.
  • the oxide composite anode material with in-situ coating of borate on the surface of the present invention is found in the half-cell test, the material not only has a higher mass specific capacity and specific energy, but the specific capacity is 1.5 to 1.5 times that of the common sodium ion battery anode material. 2 times, and the cycle life is better, it has great practical value, the sodium ion battery using the oxide composite cathode material of the surface in-situ coating borate of the present invention can be used for electric vehicles, solar power generation, wind power generation, smart Large-scale energy storage equipment for power grid peak regulation, distributed power stations, backup power supplies or communication base stations.
  • the following uses a number of specific examples to illustrate the application of several methods provided by the above-mentioned embodiments of the present invention to prepare the oxide composite positive electrode material with surface in-situ coating borate. process, and methods and battery characteristics for its application to sodium-ion secondary batteries.
  • a lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface was prepared by a solid-state method, and the same method was used to prepare a lithium-containing layered oxide material for comparison.
  • the preparation process for the lithium-containing layered oxide material in this example includes:
  • Na 2 CO 3 (analytical pure), Li 2 CO 3 (analytical pure), NiO (analytical pure), CuO (analytical pure), MnO 2 (analytical pure), Fe 2 O 3 (analytical pure), TiO 2 ( Analytical pure) were mixed according to the required stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; the precursor was transferred to an Al 2 O 3 crucible, and treated in a muffle furnace at 900°C for 15 hours in an oxygen atmosphere, A black powder layered oxide material Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 was obtained, and its XRD pattern is shown in FIG. 6 .
  • the SEM image is shown in Figure 7.
  • the preparation process of the lithium-containing layered oxide composite cathode material with in-situ coating of borate on the surface comprises:
  • Na 2 CO 3 (analytical pure), Li 2 CO 3 (analytical pure), NiO (analytical pure), CuO (analytical pure), MnO 2 (analytical pure), Fe 2 O 3 (analytical pure), TiO 2 ( Analytical pure), B 2 O 3 (analytical pure) were mixed according to the required stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; the precursor was transferred to an Al 2 O 3 crucible, and the Treated at 900°C in an oxygen atmosphere for 15 hours to obtain a black powder layered oxide material 0.5wt% Li 3 BO 3 -Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 ,
  • the coating layer on the surface of the modified composite cathode material 0.5wt% Li 3 BO 3 -Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 has a needle-like structure, which inhibits the formation of residual alkali on the surface,
  • the slurry made of this material is smooth, easy to make batteries, and greatly improves the cycle stability of the material.
  • the two layered oxide materials prepared above are used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery for further comparison.
  • the specific steps are: the prepared Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 with 0.5wt% A x By O z -Na 1.0 Li 0.05 Ni 0.33 Cu 0.05 Mn 0.37 Fe 0.1 Ti 0.1 O 2 powder, respectively with acetylene black, binder polyvinylidene fluoride (PVDF) Mix according to the mass ratio of 80:10:10, add an appropriate amount of N-methylpyrrolidone (NMP) solution, grind in a dry environment at room temperature to form a slurry, and then evenly coat the slurry on the current collector aluminum foil, and After drying under an infrared lamp, cut into (8 ⁇ 8) mm 2 pole pieces. The pole pieces were dried under vacuum at 110°C for 10 hours, and then transferred to a glove box for later use.
  • NMP N
  • the assembly of the simulated battery was carried out in a glove box with an Ar atmosphere, and a CR2032 button battery was assembled with metal sodium as the counter electrode and 1M NaClO 4 /diethyl carbonate (DEC) solution as the electrolyte.
  • DEC diethyl carbonate
  • Figure 11 shows the XRD spectra before and after the comparison.
  • the layered oxide material obtained before and after being placed in the humid air is used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery, and the electrochemical charge and discharge test is carried out.
  • the preparation process and test method are the same as in Example 1, and the test voltage range is 2.0-4.3V.
  • Figure 12 shows the charge-discharge test results. From the charge-discharge curve and the reversible specific capacity, the influence of air with a humidity of 55% on the material is relatively small, which further proves that the presence of the cladding layer can improve the air stability of the material.
  • a lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface was prepared by a solid-state method, and the same method was used to prepare a lithium-containing layered oxide material for comparison.
  • the preparation process for the lithium-containing layered oxide material in this example includes:
  • the preparation process of the lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface includes:
  • the crystal structure of Na 0.67 Li 0.02 Ni 0.18 Cu 0.13 Mn 0.47 Zr 0.2 O 2 and 0.1wt% Na 3 BO 3 -Na 0.67 Li 0.02 Ni 0.18 Cu 0.13 Mn 0.47 Zr 0.2 O 2 is P2 phase layer oxide structure.
  • the layered oxide material prepared above was used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 1. The test voltage range is 2.0-4.3V, and the reversible specific capacity of the material is shown in Table 1.
  • a lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface was prepared by a solid-state method, and the same method was used to prepare a lithium-containing layered oxide material for comparison.
  • the preparation process for the lithium-containing layered oxide material in this example includes:
  • the preparation process of lithium-containing layered oxide composite cathode materials with in-situ coating of borate on the surface includes: Na 2 CO 3 (analytical pure), Li 2 CO 3 (analytical pure), NiO (analytical pure), CuO (analytical pure), MnO 2 (analytical pure), and B 2 O 3 (analytical pure) were mixed according to the required stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; the precursor was transferred to Al 2 O 3 In the porcelain boat, the tube furnace was treated in an air atmosphere at 900°C for 15 hours to obtain a black powder layered oxide material 1.0wt% LiNaB 8 O 13 -Na 0.76 Li 0.03 Ni 0.15 Cu 0.18 Mn 0.64 O 2 , and its XRD See Figure 6 for the spectrum.
  • the crystal structure of Na 0.76 Li 0.03 Ni 0.15 Cu 0.18 Mn 0.64 O 2 and 1.0wt% LiNaB 8 O 13 -Na 0.76 Li 0.03 Ni 0.15 Cu 0.18 Mn 0.64 O 2 is the oxidation of P2 phase layered structure things.
  • the layered oxide material prepared above was used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 1. The test voltage range is 2.0-4.3V, and the reversible specific capacity of the material is shown in Table 1.
  • a lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface was prepared by a solid-state method, and the same method was used to prepare a lithium-containing layered oxide material for comparison.
  • the preparation process for the lithium-containing layered oxide material in this example includes:
  • the preparation process of lithium-containing layered oxide composite cathode materials with in-situ coating of borate on the surface includes: Na 2 CO 3 (analytical pure), Li 2 CO 3 (analytical pure), NiO (analytical pure), CuO (analytical pure), MnO 2 (analytical pure), titanium dioxide (analytical pure), and B 2 O 3 (analytical pure) were mixed according to the required stoichiometric ratio; ground in an agate mortar for half an hour to obtain a precursor; the precursor Transferred to Al2O3 ceramic boats, treated in a tube furnace at 900 ° C for 15 hours in an oxygen atmosphere, to obtain a black powder layered oxide material 5.0wt% Li 1.5 Na 0.5 B 4 O 7 -Na 0.83 Li 0.06 Ni 0.20 Cu 0.13 Mn 0.56 Ti 0.05 O 2 , see Figure 6 for its XRD pattern.
  • the layered oxide material prepared above was used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 1. The test voltage range is 2.0-4.3V, and the reversible specific capacity of the material is shown in Table 1.
  • a lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface was prepared by a solid-state method, and the same method was used to prepare a lithium-containing layered oxide material for comparison.
  • the preparation process for the lithium-containing layered oxide material in this example includes:
  • the material is Na 1.0 Li 0.02 Ni 0.4 Cu 0.05 Mn 0.4 Ti 0.09 Fe 0.04 O 2 , and its XRD pattern is shown in Fig. 6 .
  • the preparation process of the lithium-containing layered oxide composite positive electrode material with in-situ coating of borate on the surface includes:
  • the layered oxide material prepared above was used as the active material of the positive electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are with embodiment 1.
  • the test voltage range is 2.0-4.3V, and the reversible specific capacity of the material is shown in Table 1.
  • the composite positive electrode material with the in-situ coating structure of borate obtained by the in-situ coating method of the present invention not only has a high capacity, but also greatly improves the cycle capacity retention rate.
  • the morphology of the coating layer changes from the original smooth surface to the needle shape, the residual alkali on the surface of the material is greatly reduced, the stability in the air is significantly improved, the conductivity of the material, the diffusion capacity of sodium ions are higher, and the charge transfer The impedance is lower, the first charge and discharge efficiency is higher, the cycle capacity is better, especially the cycle life is longer.

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Abstract

本发明涉及一种原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途，化学通式为：γAxByOz-NaaLibNicCudMneMfO2+β；材料中，Li、Ni、Cu、Mn、对过渡金属位进行掺杂取代的元素M共同占据晶体结构中的过渡金属离子位置；层状氧化物复合正极材料的空间群为P63/mmc或P63/mcm或对应结构为P2相或O3相；AxByOz为在NaaLibNicCudMn eMfO2+β表面原位生成的针状结构的包覆层,通过包覆材料前躯体与用于生成NaaLibNicCudMneMfO2+β的层状氧化物前躯体在烧结过程中生成；其中γ为包覆材料前躯体占层状氧化物前驱体的质量分数，0.1wt％≤γ≤10wt％；A为Li和/或Na。本发明的复合正极材料不仅容量高，而且由于表面针状包覆层的存在，材料表面残碱大幅减少，空气中稳定性显著提升，首次充放电效率高，循环寿命长。

Description

原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途
本申请要求于2021年11月12日提交中国专利局、申请号为202111342367.8、发明名称为“原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途”的中国专利申请的优先权。
技术领域
本发明涉及材料技术领域，尤其涉及一种原位包覆硼酸盐的氧化物复合正极材料、制备方法和用途。
背景技术
随着社会的发展与进步，人类对能源的需求量越来越大，但煤、石油、天然气等传统化石能源由于资源日渐枯竭，再加上其造成的城市环境污染和温室效应问题日益严峻，其应用逐渐受到多方面限制，因此可持续清洁能源的开发一直是各国关注的方向。但是将风能、太阳能和潮汐能等转换成电能的过程中，这些可再生能源受自然条件的限制较大，并具有明显的时间不连续性、空间分布不均匀性等特点，这导致它们提供的电力可控性和稳定性较差，不能直接输入电网使用。因此，只有配套高性能的大规模储能系统，以此解决发电与用电的时差矛盾、调节电能品质，才能确保电力系统可靠供电。当前我国能源的可持续发展对大规模储能技术需求较为迫切，同时这也是世界各国的研究热点。
目前已有的储能方式分为物理储能和化学储能。物理储能中抽水蓄能是目前使用最多，储能量最大的，但是抽水蓄能受到地理位置的限制，且建设工期较长，其它物理储能如压缩空气储能、飞轮储能等都还未成规模。电化 学储能是指通过发生可逆的化学反应来储存或释放电量，它以其高能量转换效率和功率密度、循环寿命长、建设周期短、维护成本低等优势受到人们的普遍关注。
现今阶段，电化学储能主要包括高温钠硫电池、液流电池、铅酸电池和锂离子电池等这几大类。钠硫电池Na-S电池的工作温度为300℃，金属钠和单质硫处于熔融状态，如果高温下材料破损容易在电池模块中引起火灾，因此安全问题很大，未能大规模应用。液流电池能量密度较低、体积较大。铅酸电池相对于Ni-Cd电池无记忆效应、成本低，目前一直占储能市场的绝大部分比例，应用广泛。但是其缺点也比较明显，例如铅对环境污染大、电池能量密度低、质量重、体积较大，维护费用也会增加。由于储能系统需要具有成本低廉、绿色环保、寿命长和安全性能高等特点，在众多的电化学储能材料中，锂离子二次电池和钠离子二次电池成为储能技术中比较重要的技术。
目前作为电化学储能的锂离子电池以高能量密度、高循环稳定性、长循环寿命、体积小重量轻及无污染等优点，在日常生活中得到了广泛应用。考虑到钠在元素周期表中与锂同属于碱金属元素，因此具有相似的物理化学性质。钠离子电池和锂离子电池有相似的充放电储存机制，更重要的是钠在自然界中储量丰富且分布广泛，还有很显著的价格优势。除了钠离子价格低外，钠离子电池的正负极集流体均可以使用铝箔，而锂离子电池负极只能用铜，显然铜比铝贵的多，因此原材料成本低廉且容易获得，这些优势使得钠离子电池越来越受到世界范围的广泛关注。
但目前钠离子电池还处于研究阶段，还没有商业化的钠离子电池正极材料，现在研究者对于钠离子电池的研究主要集中在层状结构的氧化物正极材料Na xMO 2(M代表3d过渡金属元素中，可包含一种或者多种，如Ti、V、Cr、Fe、Mn、Co、Ni、Cu、Nb、Ru、Mo、Zn等)。电池的基础是氧化还原反应，反应的本质是化合价有变化，即电子有转移和偏移。失电子的半反应是氧化反应，正极材料的化合价升高；得电子的半反应是还原反应，正极材料中化 合价降低。而以上介绍的钠离子电池层状氧化物正极材料中均具有可以发生氧化还原反应的过渡金属材料，且材料初始状态的可变价过渡金属处于较低的价态，但是过渡金属离子无法完全变价、容量无法完全发挥的情况仍然有很多，且这些正极材料的空气稳定性不足导致一致性不好。
发明内容
本发明实施例提供了一种具有原位包覆硼酸盐的氧化物复合正极材料、制备方法和应用。该正极材料是一种空气稳定的、高容量、高循环稳定性的材料，其包覆层的形貌特殊，在与空气接触后呈针状。该包覆层在与空气接触前平滑的附在材料表面，在与空气接触后，包覆层形貌转变为针状，使得材料表面由于与空气接触而产生的残碱大幅减少，空气中稳定性显著提升，材料的电导率、钠离子扩散能力更高，电荷转移阻抗更低，首次充放电效率更高，循环能力更佳，尤其循环寿命更长。
第一方面，本发明实施例提供了一种具有原位包覆硼酸盐的氧化物复合正极材料，所述材料的化学通式为：γA xB yO z-Na aLi bNi cCu dMn eM fO 2+β；
所述材料中，Li、Ni、Cu、Mn、M共同占据晶体结构中的过渡金属离子位置；其中M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
所述a，b，c，d，e，f，2+β分别为对应元素所占的摩尔百分比，化学通式中各组分满足电荷守恒和化学计量守恒；其中，b+c+d+e+f＝1，且a+b+2c+2d+4e+mf＝2(2+β)；0.67≤a≤1；0＜b≤0.2；0＜c≤0.65；0＜d≤0.28；0＜e≤0.65；-0.05≤β≤0.05；m为M的化合价态；
所述层状氧化物复合正极材料的空间群为P63/mmc或P63/mcm或
Figure PCTCN2022079725-appb-000001
对应结构为P2相或O3相；
所述A xB yO z为在Na aLi bNi cCu dMn eM fO 2+β表面原位生成的针状结构的包覆 层,通过包覆材料前驱体与用于生成Na aLi bNi cCu dMn eM fO 2+β的层状氧化物前驱体在烧结过程中生成；其中γ为包覆材料前躯体占层状氧化物前驱体的质量分数，0.1wt％≤γ≤10wt％；A为Li和/或Na，0＜x≤3，0＜y≤10，0＜z≤15。
优选的，所述包覆材料前躯体为氧化硼或硼酸；熔融态的包覆材料前驱体与层状氧化物前驱体中的一部分钠盐和/或锂盐形成A xB yO z。
第二方面，本发明实施例提供了一种第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，所述方法为固相法，包括：
将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂，镍、铜、锰的氧化物，所需化学计量的M的氧化物或碳酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
采用球磨的方法将所述正极材料前驱体均匀混合得到前驱体粉末；
将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
第三方面，本发明实施例提供了一种第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，所述方法为喷雾干燥法，包括：
将层状氧化物前躯体和占所述层状氧化物前驱体总质量的 0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠或硝酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂或硝酸钠锂，镍、铜、锰的氧化物或硝酸盐，所需化学计量的M的氧化物或碳酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
将所述正极材料前驱体加乙醇或水后搅拌均匀形成浆料；
对所述浆料进行喷雾干燥后得到前驱体粉末；
将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
第四方面，本发明实施例提供了一种第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，所述方法为燃烧法，包括：
将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的硝酸钠，所需钠的化学计量100wt％～110wt％的硝酸锂，镍、铜、锰的硝酸盐，所需化学计量的M的硝酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
将所述正极材料前驱体加乙酰丙酮搅拌均匀形成浆料；
对所述浆料进行干燥后得到前驱体粉末；
将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
第五方面，本发明实施例提供了一种第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，所述方法为溶胶-凝胶法，包括：
将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的钠盐，所需钠的化学计量100wt％～110wt％的锂盐，镍、铜、锰的硝酸盐或硫酸盐，所需化学计量的M的硝酸盐或硫酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；所述钠盐包括：乙酸钠、硝酸钠、碳酸钠或硫酸钠中的一种或几种；所述锂盐包括：乙酸锂、硝酸锂、碳酸锂或硫酸锂中的一种或几种；
在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
将所述前驱体凝胶置于坩埚中，在200℃～500℃的空气气氛下，预烧2个小时；
将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的 氧化物复合正极材料。
第六方面，本发明实施例提供了一种第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，所述方法为共沉淀法，包括：
将所需化学计量的镍、铜、锰、锂和M的硝酸盐按比例溶于水混合成前驱体溶液；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
用蠕动泵将所述前驱体溶液滴加在氨水溶液中，生成沉淀物；
将得到的沉淀物用去离子水清洗干净，烘干后将所述沉淀物与碳酸钠、占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按照化学计量比均匀混合得到的前驱物；所述层状氧化物前驱体包括所述碳酸钠和所述镍、铜、锰、锂、M的硝酸盐；
将所述前驱物置于坩埚或瓷舟中，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
第七方面，本发明实施例提供了一种钠离子二次电池的正极极片，所述正极极片包括：
集流体、涂覆于所述集流体之上的导电添加剂和粘结剂，和上述第一方面所述的具有原位包覆硼酸盐的氧化物复合正极材料。
第八方面，本发明实施例提供了一种上述第七方面所述的正极极片的钠离子二次电池。
第九方面，本发明实施例提供了一种钠离子二次电池的用途，所述钠离子二次电池用于电动汽车、太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
本发明提出的具有原位包覆硼酸盐的氧化物复合正极材料，通过氧化硼或硼酸在较低的温度下融化，与正极材料前驱体中部分钠盐、锂盐形成化学通式为A xB yO z的硼酸锂盐或硼酸钠盐，均匀、完整地包裹着含锂层状氧化物正极。A xB yO z与空气接触后转变为针状结构，使得材料表面由于与空气接触而产生的残碱大幅减少，空气中稳定性显著提升，材料的电导率、钠离子扩散能力更高，电荷转移阻抗更低，首次充放电效率更高，循环能力更加，因而使得表面原位包覆硼酸盐的含锂氧化物复合正极材料具有空气稳定、高容量、高循环稳定性的特性，这种材料可以在45％RH-60％RH空气中放置48小时以上仍然保持结构稳定。
附图说明
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例提供的固相法制备表面原位包覆硼酸盐的氧化物复合正极材料的制备方法流程图；
图2为本发明实施例提供的喷雾干燥法制备表面原位包覆硼酸盐的氧化物复合正极材料的制备方法流程图；
图3为本发明实施例提供的燃烧法制备表面原位包覆硼酸盐的氧化物复合正极材料的制备方法流程图；
图4为本发明实施例提供的溶胶-凝胶法制备表面原位包覆硼酸盐的氧化物复合正极材料的制备方法流程图；
图5为本发明实施例提供的共沉淀法制备表面原位包覆硼酸盐的氧化物复合正极材料的制备方法流程图；
图6为本发明实施例提供的不同元素摩尔百分比的多个表面原位包覆硼酸盐的氧化物复合正极材料的XRD图谱；
图7为本发明实施例1提供的固相法合成的用于对本例的Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2材料的SEM图；
图8为本发明实施例1提供的固相法合成的0.5wt％Li 3BO 3-Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2材料的SEM图；
图9为本发明实施例1提供的如上所述的两种材料制备的钠离子电池在2.0-4.3V充放电曲线对比图；
图10为本发明实施例1提供的如上所述的两种材料制备的钠离子电池循环曲线对比图；
图11为本发明实施例1提供的表面原位包覆硼酸盐的氧化物复合正极材料在湿度为55％的空气中放置48小时前后的XRD谱图；
图12为本发明实施例1提供的表面原位包覆硼酸盐的氧化物复合正极材料在湿度为55％的空气中放置48小时前后的两种材料制备的钠离子电池在2.0-4.3V充放电曲线对比图。
具体实施方式
下面通过附图和具体的实施例，对本发明进行进一步的说明，但应当理解为这些实施例仅仅是用于更详细说明之用，而不应理解为用以任何形式限制本发明，即并不意于限制本发明的保护范围。
本发明实施例提出了一种具有表面原位包覆硼酸盐的、空气稳定的、高容量、高循环稳定性的层状含锂氧化物复合正极材料，该材料的化学通式为：γA xB yO z-Na aLi bNi cCu dMn eM fO 2+β；该层状氧化物复合正极材料的空间群为P63/mmc或P63/mcm或
Figure PCTCN2022079725-appb-000002
对应结构为P2相或O3相。
在上述材料中，Li、Ni、Cu、Mn、M共同占据晶体结构中的过渡金属离子位置；其中M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
a，b，c，d，e，f，2+β分别为对应元素所占的摩尔百分比，化学通式中各组分满足电荷守恒和化学计量守恒；其中，b+c+d+e+f＝1，且 a+b+2c+2d+4e+mf＝2(2+β)；0.67≤a≤1；0＜b≤0.2；0＜c≤0.65；0＜d≤0.28；0＜e≤0.65；-0.05≤β≤0.05；m为M的化合价态；
A xB yO z为在Na aLi bNi cCu dMn eM fO 2+β表面原位生成的包覆层,通过包覆材料前躯体与用于生成Na aLi bNi cCu dMn eM fO 2+β的层状氧化物前躯体在烧结过程中生成；包覆材料前躯体为氧化硼或硼酸；熔融态的包覆材料前躯体与层状氧化物前驱体中的一部分钠盐和/或锂盐形成A xB yO z。γ为包覆材料前躯体占层状氧化物前驱体的质量分数，0.1wt％≤γ≤10wt％；A为Li和/或Na，0＜x≤3，0＜y≤10，0＜z≤15。该包覆层形貌特殊，在与空气接触后呈针状。该包覆层在与空气接触前平滑的附在材料表面，由于材料无法避免的在制作极片的过程中会与空气接触，包覆层形貌转变为针状，材料表面残碱大幅减少，空气中稳定性显著提升，材料的电导率、钠离子扩散能力更高，电荷转移阻抗更低，首次充放电效率更高，循环能力更加，尤其循环寿命更长。
本发明的具有表面原位包覆硼酸盐的氧化物复合正极材料的制备方法可兼容多种工艺方法，以下逐一进行说明。
具有表面原位包覆硼酸盐的氧化物复合正极材料可通过固相法制备得到，主要步骤如图1所示，包括：
步骤110，将层状氧化物前躯体和占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；
其中，包覆材料前躯体为氧化硼或硼酸；层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂，镍、铜、锰的氧化物，所需化学计量的M的氧化物或碳酸盐；M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
步骤120，采用球磨的方法将正极材料前驱体均匀混合得到前驱体粉末；
步骤130，将前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
步骤140，将热处理后所得粉末进行研磨，得到具有表面原位包覆硼酸盐的氧化物复合正极材料。
具有表面原位包覆硼酸盐的氧化物复合正极材料可通过喷雾干燥法制备得到，主要步骤如图2所示，包括：
步骤210，将层状氧化物前躯体和占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；
其中，包覆材料前躯体为氧化硼或硼酸；层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠或硝酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂，镍、铜、锰的氧化物或硝酸盐，所需化学计量的M的氧化物或碳酸盐；M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
步骤220，将正极材料前驱体加乙醇或水后搅拌均匀形成浆料；
步骤230，对浆料进行喷雾干燥后得到前驱体粉末；
步骤240，将前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
步骤250，将热处理后所得粉末进行研磨，得到具有表面原位包覆硼酸盐的氧化物复合正极材料。
具有表面原位包覆硼酸盐的氧化物复合正极材料可通过燃烧法制备得到，主要步骤如图3所示，包括：
步骤310，将层状氧化物前躯体和占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；
其中，包覆材料前躯体为氧化硼或硼酸；层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的硝酸钠，所需钠的化学计量100wt％～110wt％的硝酸锂，镍、铜、锰的硝酸盐；M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
步骤320，将正极材料前驱体加乙酰丙酮搅拌均匀形成浆料；
步骤330，对浆料进行干燥后得到前驱体粉末；
具体的，干燥优选为在在80℃下进行干燥。
步骤340，将前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
步骤350，将热处理后所得粉末进行研磨，得到具有表面原位包覆硼酸盐的氧化物复合正极材料。
具有表面原位包覆硼酸盐的氧化物复合正极材料可通过溶胶-凝胶法制备得到，主要步骤如图4所示，包括：
步骤410，将层状氧化物前躯体和占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；
其中，包覆材料前躯体为氧化硼或硼酸；层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的钠盐，所需钠的化学计量100wt％～110wt％的锂盐，镍、铜、锰的硝酸盐或硫酸盐；M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；钠盐包括：乙酸钠、硝酸钠、碳酸钠或硫酸钠中的一种或几种；锂盐包括：乙酸锂、 硝酸锂、碳酸锂或硫酸锂中的一种或几种；
步骤420，在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
步骤430，将前驱体凝胶置于坩埚中，在200℃～500℃的空气气氛下，预烧2个小时；
步骤440，将前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
步骤450，将热处理后所得粉末进行研磨，得到具有表面原位包覆硼酸盐的氧化物复合正极材料。
具有表面原位包覆硼酸盐的氧化物复合正极材料可通过共沉淀法制备得到，主要步骤如图5所示，包括：
步骤510，将所需化学计量的镍、铜、锰、锂和M的硝酸盐按比例溶于水混合成前驱体溶液；
其中，M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
步骤520，用蠕动泵将前驱体溶液滴加在氨水溶液中，生成沉淀物；
步骤530，将得到的沉淀物用去离子水清洗干净，烘干后将沉淀物与碳酸钠、占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按照化学计量比均匀混合得到的前驱物；
其中，层状氧化物前驱体包括碳酸钠和镍、铜、锰、锂、M的硝酸盐；
步骤540，将前驱物置于坩埚或瓷舟中，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
步骤550，将热处理后所得粉末进行研磨，得到具有表面原位包覆硼 酸盐的氧化物复合正极材料。
以上各制备方法，能够用于制备上述实施例中的具有表面原位包覆硼酸盐的层状含锂氧化物复合正极材料材料。本实施例提供的方法简单易行、所含有的元素钠、锂、镍、铜和锰等都是无毒安全的元素，在地壳中的丰度高，因此制造成本低廉所用材料安全无毒，适用于大规模制造的应用。
本发明的表面原位包覆硼酸盐的氧化物复合正极材料在半电池测试中发现，该材料不但具有较高的质量比容量和比能量，比容量是普通钠离子电池正极材料的1.5到2倍，且循环寿命较好，具有很大实用价值，应用本发明的表面原位包覆硼酸盐的氧化物复合正极材料的钠离子电池可以用于电动汽车、太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施例提供的几种方法制备具有表面原位包覆硼酸盐的氧化物复合正极材料的具体过程，以及将其应用于钠离子二次电池的方法和电池特性。
实施例1
本实施例中采用固相法制备具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料，并应用同样方法制备含锂层状氧化物材料，以进行对比。
用于对本例的含锂层状氧化物材料的制备过程包括：
将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、Fe 2O 3(分析纯)、TiO 2(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2，其XRD图谱参见图6。SEM图见图7。
具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料的制备过 程包括：
将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、Fe 2O 3(分析纯)、TiO 2(分析纯)、B 2O 3(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料0.5wt％Li 3BO 3-Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2，
其XRD图谱参见图6。SEM图见图8。
从XRD图谱上看，Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2与0.5wt％Li 3BO 3-Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2的晶体结构为O3相层状结构的氧化物。
从图7图8两个SEM图中可以看出，原始材料Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2存在很多块状的残碱，这会导致浆料结块，这对后续电池的制作造成了困难，并且导致材料的电导率、钠离子扩散能力下降，电荷转移阻抗升高，首次充放电效率降低，电池的循环稳定性也有一定的影响。而改性后的复合正极材料0.5wt％Li 3BO 3-Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2表面的包覆层为针状结构，抑制了表面残碱的生成，用这种材料制作浆料顺滑，便于制作电池，并且大大提升了材料的循环稳定性。
将上述制备得到的两种层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，以进行进一步对比，具体步骤为：将制备好的Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2与0.5wt％A xB yO z-Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2粉末，分别与乙炔黑、粘结剂聚偏氟乙烯(PVDF)按照80:10:10的质量比混合，加入适量的N-甲基吡咯烷酮(NMP)溶液，在常温干燥的环境中研磨形成浆料，然后把浆料均匀涂覆于集流体铝箔上，并在红外灯下干燥后，裁成(8×8)mm 2的极片。极片在真空条件下，110℃干燥10小时，随即转移到手套箱备用。
模拟电池的装配在Ar气氛的手套箱内进行，以金属钠作为对电极，以1M NaClO 4/碳酸二乙酯(DEC)溶液作为电解液，装配成CR2032扣式电池。使用恒流充放电模式，在C/10以及C/2电流密度下进行充放电测试。在放电截至电压为2.0V，充电截至电压为4.3V的条件下，在2.0-4.3V充放电测试结果见图9，电池循环曲线见图10，可以看出，虽然用于对本例的Na 1.0Li 0.05Ni 0.33Cu 0.05Mn 0.37Fe 0.1Ti 0.1O 2材料的首周放电容量达到了178.2mAh/g，而原位包覆硼酸盐的正极材料(图中记为原位包覆材料，下同)获得了更高的首周库伦效率，以及更高的循环稳定性。
此外，我们还对本实施例1制备所得的表面原位包覆硼酸盐的氧化物复合正极材料在湿度为55％的空气中放置48小时前后进行对比，图11为对比前后的XRD谱图，将上述潮湿空气中放置前后得到的层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例1，测试电压范围为2.0～4.3V，图12为其充放电测试结果，从充放电曲线以及可逆比容量上来看，湿度为55％的空气对材料的影响比较小，进一步证明了包覆层的存在可以提升材料的空气稳定性。
实施例2
本实施例中采用固相法制备具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料，并应用同样方法制备含锂层状氧化物材料，以进行对比。
用于对本例的含锂层状氧化物材料的制备过程包括：
将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、ZrO 2(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料Na 0.67Li 0.02Ni 0.18Cu 0.13Mn 0.47Zr 0.2O 2，其XRD图谱参见图6。具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料的制备过程包括：
将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、ZrO 2(分析纯)、B 2O 3(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料0.1wt％Na 3BO 3-Na 0.67Li 0.02Ni 0.18Cu 0.13Mn 0.47Zr 0.2O 2,其XRD图谱参见图6。
从XRD图谱上看,Na 0.67Li 0.02Ni 0.18Cu 0.13Mn 0.47Zr 0.2O 2与0.1wt％Na 3BO 3-Na 0.67Li 0.02Ni 0.18Cu 0.13Mn 0.47Zr 0.2O 2的晶体结构为P2相层状结构的氧化物。
将上述制备得到的层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例1。测试电压范围为2.0～4.3V，材料的可逆比容量如表1。
实施例3
本实施例中采用固相法制备具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料，并应用同样方法制备含锂层状氧化物材料，以进行对比。
用于对本例的含锂层状氧化物材料的制备过程包括：
将将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料Na 0.76Li 0.03Ni 0.15Cu 0.18Mn 0.64O 2，其XRD图谱参见图6。
具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料的制备过程包括：将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、B 2O 3(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3瓷舟内，在管式炉中空气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料 1.0wt％LiNaB 8O 13-Na 0.76Li 0.03Ni 0.15Cu 0.18Mn 0.64O 2,其XRD图谱参见图6。
从XRD图谱上看,Na 0.76Li 0.03Ni 0.15Cu 0.18Mn 0.64O 2与1.0wt％LiNaB 8O 13-Na 0.76Li 0.03Ni 0.15Cu 0.18Mn 0.64O 2的晶体结构为P2相层状结构的氧化物。
将上述制备得到的层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例1。测试电压范围为2.0～4.3V，材料的可逆比容量如表1。
实施例4
本实施例中采用固相法制备具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料，并应用同样方法制备含锂层状氧化物材料，以进行对比。
用于对本例的含锂层状氧化物材料的制备过程包括：
将将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、二氧化钛(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料Na 0.83Li 0.06Ni 0.20Cu 0.13Mn 0.56Ti 0.05O 2，其XRD图谱参见图6。
具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料的制备过程包括：将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、二氧化钛(分析纯)、B 2O 3(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3瓷舟内，在管式炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料5.0wt％Li 1.5Na 0.5B 4O 7-Na 0.83Li 0.06Ni 0.20Cu 0.13Mn 0.56Ti 0.05O 2,其XRD图谱参见图6。
从XRD图谱上看,Na 0.83Li 0.06Ni 0.20Cu 0.13Mn 0.56Ti 0.05O 2与5.0wt％Li 1.5Na 0.5B 4O 7-Na 0.83Li 0.06Ni 0.20Cu 0.13Mn 0.56Ti 0.05O 2的晶体结构为O3状结构的 氧化物。
将上述制备得到的层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例1。测试电压范围为2.0～4.3V，材料的可逆比容量如表1。
实施例5
本实施例中采用固相法制备具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料，并应用同样方法制备含锂层状氧化物材料，以进行对比。
用于对本例的含锂层状氧化物材料的制备过程包括：
将将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、TiO 2(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3坩埚内，在马弗炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料Na 1.0Li 0.02Ni 0.4Cu 0.05Mn 0.4Ti 0.09Fe 0.04O 2，其XRD图谱参见图6。
具有表面原位包覆硼酸盐的含锂层状氧化物复合正极材料的制备过程包括：
将Na 2CO 3(分析纯)、Li 2CO 3(分析纯)、NiO(分析纯)、CuO(分析纯)、MnO 2(分析纯)、氧化铝(分析纯)、B 2O 3(分析纯)按所需化学计量比混合；在玛瑙研钵中研磨半小时，得到前驱体；将前驱体转移到Al 2O 3瓷舟内，在管式炉中氧气氛围900℃下处理15小时，得到黑色粉末的层状氧化物材料10wt％Li 0.2Na 0.8BO 2-Na 1.0Li 0.02Ni 0.4Cu 0.05Mn 0.4Ti 0.09Fe 0.04O 2,其XRD图谱参见图6。
从XRD图谱上看,Na 1.0Li 0.02Ni 0.4Cu 0.05Mn 0.4Ti 0.09Fe 0.04O 2与10wt％Li 0.2Na 0.8BO 2-Na 1.0Li 0.02Ni 0.4Cu 0.05Mn 0.4Ti 0.09Fe 0.04O 2的晶体结构为O3状结构的氧化物。
将上述制备得到的层状氧化物材料作为电池正极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实 施例1。测试电压范围为2.0～4.3V，材料的可逆比容量如表1。
Figure PCTCN2022079725-appb-000003
表1
通过对比可以看出，本发明这种原位包覆的方式得到的具有原位包覆硼酸盐的包覆结构的复合正极材料不仅容量高，而且循环容量保持率大幅提升。由于材料与空气接触后，包覆层形貌由原本表面光滑转变为针状，材料表面的残碱大幅减少，空气中稳定性显著提升，材料的电导率、钠离子扩散能力更高，电荷转移阻抗更低，首次充放电效率更高，循环能力更加，尤其循环寿命更长。
虽然以上实施例仅以固相法为例对本发明方案的具体实施进行了详细说明，但在前面提供的喷雾干燥法、燃烧法、溶胶-凝胶法和共沉淀法的制备 方法，均为本领域技术人员所熟知的方法，本领域技术人员根据本发明提供的以上制备方法的制备流程步骤，可以在不付出创造性劳动的前提下即可实现本发明的技术方案。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种具有原位包覆硼酸盐的氧化物复合正极材料，其特征在于，所述材料的化学通式为：γA xB yO z-Na aLi bNi cCu dMn eM fO 2+β；
    所述材料中，Li、Ni、Cu、Mn、M共同占据晶体结构中的过渡金属离子位置；其中M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
    所述a，b，c，d，e，f，2+β分别为对应元素所占的摩尔百分比，化学通式中各组分满足电荷守恒和化学计量守恒；其中，b+c+d+e+f＝1，且a+b+2c+2d+4e+mf＝2(2+β)；0.67≤a≤1；0＜b≤0.2；0＜c≤0.65；0＜d≤0.28；0＜e≤0.65；-0.05≤β≤0.05；m为M的化合价态；
    所述层状氧化物复合正极材料的空间群为P63/mmc或P63/mcm或
    Figure PCTCN2022079725-appb-100001
    对应结构为P2相或O3相；
    所述A xB yO z为在Na aLi bNi cCu dMn eM fO 2+β表面原位生成的针状结构的包覆层,通过包覆材料前躯体与用于生成Na aLi bNi cCu dMn eM fO 2+β的层状氧化物前躯体在烧结过程中生成；其中γ为包覆材料前躯体占层状氧化物前驱体的质量分数，0.1wt％≤γ≤10wt％；A为Li和/或Na，0＜x≤3，0＜y≤10，0＜z≤15。
  2. 根据权利要求1所述的具有原位包覆硼酸盐的氧化物复合正极材料，其特征在于，所述包覆材料前躯体为氧化硼或硼酸；熔融态的包覆材料前躯体与层状氧化物前驱体中的一部分钠盐和/或锂盐形成A xB yO z。
  3. 一种上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，其特征在于，所述方法为固相法，包括：
    将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所 述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂，镍、铜、锰的氧化物，所需化学计量的M的氧化物或碳酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
    采用球磨的方法将所述正极材料前驱体均匀混合得到前驱体粉末；
    将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
    将热处理后所得粉末进行研磨，得到所述具有原位包覆硼酸盐的氧化物复合正极材料。
  4. 一种上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，其特征在于，所述方法为喷雾干燥法，包括：
    将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的碳酸钠或硝酸钠，所需钠的化学计量100wt％～110wt％的碳酸锂，镍、铜、锰的氧化物或硝酸盐，所需化学计量的M的氧化物或碳酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
    将所述正极材料前驱体加乙醇或水后搅拌均匀形成浆料；
    对所述浆料进行喷雾干燥后得到前驱体粉末；
    将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或 氧气气氛中热处理2～24小时；
    将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
  5. 一种上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，其特征在于，所述方法为燃烧法，包括：
    将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠的化学计量100wt％～110wt％的硝酸钠，所需钠的化学计量100wt％～110wt％的硝酸锂，镍、铜、锰的硝酸盐，所需化学计量的M的硝酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
    将所述正极材料前驱体加乙酰丙酮搅拌均匀形成浆料；
    对所述浆料进行干燥后得到前驱体粉末；
    将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
    将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
  6. 一种上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，其特征在于，所述方法为溶胶-凝胶法，包括：
    将层状氧化物前躯体和占所述层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按比例混合成正极材料前驱体；其中，所述包覆材料前躯体为氧化硼或硼酸；所述层状氧化物前躯体包括：所需钠 的化学计量100wt％～110wt％的钠盐，所需钠的化学计量100wt％～110wt％的锂盐，镍、铜、锰的硝酸盐或硫酸盐，所需化学计量的M的硝酸盐或硫酸盐；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；所述钠盐包括：乙酸钠、硝酸钠、碳酸钠或硫酸钠中的一种或几种；所述锂盐包括：乙酸锂、硝酸锂、碳酸锂或硫酸锂中的一种或几种；
    在50℃～100℃下搅拌，并且加入适量螯合剂，蒸干形成前驱体凝胶；
    将所述前驱体凝胶置于坩埚中，在200℃～500℃的空气气氛下，预烧2个小时；
    将所述前驱体粉末置于马弗炉或管式炉内，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
    将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
  7. 一种上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料的制备方法，其特征在于，所述方法为共沉淀法，包括：
    将所需化学计量的镍、铜、锰、锂和M的硝酸盐按比例溶于水混合成前驱体溶液；所述M为对过渡金属位进行掺杂取代的元素，包括ⅢA族、Ⅳ主族、VA族或VIA族的非金属元素中的一种或多种以及第四周期和第五周期的过渡金属元素中的一种或多种；
    用蠕动泵将所述前驱体溶液滴加在氨水溶液中，生成沉淀物；
    将得到的沉淀物用去离子水清洗干净，烘干后将所述沉淀物与碳酸钠、占层状氧化物前驱体总质量的0.1wt％～10wt％的包覆材料前躯体按照化学计量比均匀混合得到的前驱物；所述层状氧化物前驱体包括所述碳酸钠 和所述镍、铜、锰、锂、M的硝酸盐；
    将所述前驱物置于坩埚或瓷舟中，在600℃～1000℃的空气或氧气气氛中热处理2～24小时；
    将热处理后所得粉末进行研磨，得到所述具有表面原位包覆硼酸盐的氧化物复合正极材料。
  8. 一种钠离子二次电池的正极极片，其特征在于，所述正极极片包括：
    集流体、涂覆于所述集流体之上的导电添加剂和粘结剂，和上述权利要求1或2所述的具有原位包覆硼酸盐的氧化物复合正极材料。
  9. 一种包括上述权利要求8所述的正极极片的钠离子二次电池。
  10. 一种如上述权利要求9所述的钠离子二次电池的用途，其特征在于，所述钠离子二次电池用于电动汽车、太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115924931A (zh) * 2023-01-06 2023-04-07 中国科学院新疆理化技术研究所 一种化合物硼酸锂钠及制备方法和用途
CN116588992A (zh) * 2023-07-14 2023-08-15 兰溪博观循环科技有限公司 硼磷酸盐与焦磷酸盐包覆改性的前驱体及其制备方法、应用
CN117352743A (zh) * 2023-12-01 2024-01-05 宁德时代新能源科技股份有限公司 钠离子电池正极材料及其制备方法、正极极片及电池和用电装置
CN117383627A (zh) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 钠电层状正极材料的制备方法
WO2024092314A1 (en) * 2022-11-04 2024-05-10 University Of Technology Sydney Cathode materials

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116750802A (zh) * 2023-08-21 2023-09-15 中节能万润股份有限公司 一种层状氧化物钠离子电池正极材料制备方法及应用
CN117334887A (zh) * 2023-12-01 2024-01-02 宜宾锂宝新材料有限公司 一种层状氧化物复合正极材料及其制备方法和钠电池

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010129509A (ja) * 2008-12-01 2010-06-10 Sanyo Electric Co Ltd 非水電解質電池
CN104795561A (zh) * 2014-07-25 2015-07-22 中国科学院物理研究所 一种层状o3相含镍氧化物正极材料及其制备方法和用途
CN105244492A (zh) * 2014-07-11 2016-01-13 北京当升材料科技股份有限公司 一种含硼锂离子电池正极材料及其制备方法
CN105470493A (zh) * 2014-08-19 2016-04-06 神华集团有限责任公司 一种材料及其制备以及含有该材料的锂离子正极活性物质、正极材料、电池正极和电池
CN109560258A (zh) * 2017-09-26 2019-04-02 中国科学院物理研究所 一种阴离子变价层状氧化物材料、制备方法和用途
CN109817914A (zh) * 2019-01-17 2019-05-28 中国科学院宁波材料技术与工程研究所 一种低表面残碱的正极材料及其制备方法与应用
CN111162250A (zh) * 2018-11-07 2020-05-15 中国科学院物理研究所 纯阳离子变价的高钠含量p2相层状氧化物材料、制备方法和用途
CN112928252A (zh) * 2021-01-22 2021-06-08 中国科学院过程工程研究所 一种钠离子电池正极材料及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010129509A (ja) * 2008-12-01 2010-06-10 Sanyo Electric Co Ltd 非水電解質電池
CN105244492A (zh) * 2014-07-11 2016-01-13 北京当升材料科技股份有限公司 一种含硼锂离子电池正极材料及其制备方法
CN104795561A (zh) * 2014-07-25 2015-07-22 中国科学院物理研究所 一种层状o3相含镍氧化物正极材料及其制备方法和用途
CN105470493A (zh) * 2014-08-19 2016-04-06 神华集团有限责任公司 一种材料及其制备以及含有该材料的锂离子正极活性物质、正极材料、电池正极和电池
CN109560258A (zh) * 2017-09-26 2019-04-02 中国科学院物理研究所 一种阴离子变价层状氧化物材料、制备方法和用途
CN111162250A (zh) * 2018-11-07 2020-05-15 中国科学院物理研究所 纯阳离子变价的高钠含量p2相层状氧化物材料、制备方法和用途
CN109817914A (zh) * 2019-01-17 2019-05-28 中国科学院宁波材料技术与工程研究所 一种低表面残碱的正极材料及其制备方法与应用
CN112928252A (zh) * 2021-01-22 2021-06-08 中国科学院过程工程研究所 一种钠离子电池正极材料及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MU, LINQIN ET AL.: "Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode", ADVANCED MATERIALS, vol. 27, 5 October 2015 (2015-10-05), XP055268591, DOI: 10.1002/adma.201502449 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024092314A1 (en) * 2022-11-04 2024-05-10 University Of Technology Sydney Cathode materials
CN115924931A (zh) * 2023-01-06 2023-04-07 中国科学院新疆理化技术研究所 一种化合物硼酸锂钠及制备方法和用途
CN116588992A (zh) * 2023-07-14 2023-08-15 兰溪博观循环科技有限公司 硼磷酸盐与焦磷酸盐包覆改性的前驱体及其制备方法、应用
CN116588992B (zh) * 2023-07-14 2023-10-24 兰溪博观循环科技有限公司 硼磷酸盐与焦磷酸盐包覆改性的前驱体及其制备方法、应用
CN117352743A (zh) * 2023-12-01 2024-01-05 宁德时代新能源科技股份有限公司 钠离子电池正极材料及其制备方法、正极极片及电池和用电装置
CN117352743B (zh) * 2023-12-01 2024-04-12 宁德时代新能源科技股份有限公司 钠离子电池正极材料及其制备方法、正极极片及电池和用电装置
CN117383627A (zh) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 钠电层状正极材料的制备方法
CN117383627B (zh) * 2023-12-13 2024-03-12 泾河新城陕煤技术研究院新能源材料有限公司 钠电层状正极材料的制备方法

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