WO2024022431A1 - 钠离子电池正极材料及其制备方法和应用 - Google Patents

钠离子电池正极材料及其制备方法和应用 Download PDF

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WO2024022431A1
WO2024022431A1 PCT/CN2023/109516 CN2023109516W WO2024022431A1 WO 2024022431 A1 WO2024022431 A1 WO 2024022431A1 CN 2023109516 W CN2023109516 W CN 2023109516W WO 2024022431 A1 WO2024022431 A1 WO 2024022431A1
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sodium
ion battery
battery cathode
cathode material
preparation
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PCT/CN2023/109516
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English (en)
French (fr)
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王勤
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湖北万润新能源科技股份有限公司
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Priority to KR1020247011435A priority Critical patent/KR20240056745A/ko
Priority to EP23845638.8A priority patent/EP4394932A1/en
Publication of WO2024022431A1 publication Critical patent/WO2024022431A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • C01B35/128—Borates containing plural metal or metal and ammonium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • 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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of sodium ion batteries, and in particular to a sodium ion battery cathode material and its preparation method and application.
  • lithium batteries also use another rare metal - cobalt (Co).
  • EV electric vehicle
  • Scarce energy sources such as lithium and cobalt will inevitably face reduced resources and rising prices.
  • sodium has an abundance of 2.3% to 2.8%, 4 to 5 orders of magnitude higher than lithium, and has similar physical and chemical properties to lithium. Therefore, sodium-ion batteries have been widely used. focus on.
  • sodium-ion batteries known as "post-lithium batteries” had been proposed and started almost at the same time as lithium-ion batteries.
  • post-lithium batteries sodium-ion battery research gradually downplayed.
  • the electrode materials successfully used in lithium-ion batteries were simply applied to sodium-ion batteries. The difference in material lattice structure requirements between sodium-ion batteries and lithium-ion batteries was not considered, resulting in poor performance of sodium-ion batteries.
  • layered sodium oxide battery materials have the advantage of high energy density, but their cycle performance is very poor.
  • the energy density of Prussian blue structure sodium battery materials is still low, the structure is unstable, and there are toxic and harmful raw materials.
  • Polyanionic sodium battery materials have the advantages of stable structure and long cycle life, but generally have low capacity and low energy density.
  • the first object of the present invention is to provide a method for preparing a sodium-ion battery cathode material.
  • the method has simple steps and low cost.
  • the prepared sodium-ion battery cathode material has good conductivity, high capacity and energy. High density and other characteristics.
  • the second object of the present invention is to provide a sodium-ion battery cathode material, which is prepared by the above-mentioned preparation method of a sodium-ion battery cathode material.
  • the third object of the present invention is to provide a sodium-ion battery, including the sodium-ion battery cathode material as described above.
  • the invention provides a method for preparing a sodium ion battery cathode material, which includes the following steps:
  • the invention also provides a sodium-ion battery cathode material, which is prepared by the above-mentioned preparation method of the sodium-ion battery cathode material.
  • the present invention also provides a sodium ion battery, including the sodium ion battery cathode material as described above.
  • the preparation method of the sodium ion battery cathode material provided by the present invention can greatly improve the ionic conductivity and electronic conductivity through the doping of metal ions and the wrapping of sodium vanadate and carbon, and can appropriately increase the size of the sodium ion battery cathode material.
  • the primary particle size increases the compaction density and resistance to oxygen and moisture, so that the energy density of the prepared sodium-ion battery cathode material is close to that of the lithium iron phosphate material, up to 170wh/kg, and the cost is also lower than that of the lithium iron phosphate material. Lithium iron phosphate materials are much lower.
  • the sodium ion battery cathode material prepared by the preparation method of the sodium ion battery cathode material of the present invention uses the polyanionic sodium battery material, that is, sodium manganese iron borate as the core, and sodium vanadate and carbon are simultaneously coated in the polyanionic sodium battery material. on the surface, thereby forming a protective layer.
  • sodium vanadate can protect the core polyanionic battery material from contact with oxygen and moisture, and is beneficial to improving ion conductivity and electronic conductivity, capacity and cycle performance.
  • Carbon can The electronic conductivity is further improved, allowing the sodium-ion battery cathode material to have excellent electrochemical properties.
  • Figure 1 is an SEM image of ferromanganese (II) hydroxide prepared in Example 1 of the present invention.
  • Figure 2 is an SEM image of the first calcined material prepared in Example 1 of the present invention.
  • Figure 3 is an SEM image of the spray material prepared in Example 1 of the present invention.
  • Figure 4 is an SEM image of the sodium ion battery cathode material prepared in Example 1 of the present invention.
  • Figure 5 is a graph showing the relationship between the capacity retention rate and the number of cycles of the sodium-ion battery cathode material prepared in Example 1 of the present invention.
  • Figure 6 is a charge-discharge curve of the sodium-ion battery cathode material prepared in Example 1 of the present invention.
  • Figure 7 is a DC resistance diagram of the sodium-ion battery cathode material prepared in Example 1 of the present invention when the capacity remains at 50%.
  • a method for preparing a sodium ion battery cathode material which includes the following steps:
  • the present invention provides a method for preparing a cathode material for a sodium ion battery, by using sodium borohydride and ferric manganese (II) hydroxide to prepare the first calcined material, that is, sodium ferric manganese borate (Na(Fe,Mn)BO 3 );
  • sodium borohydride is used as a boron source and sodium source, and sodium borohydride is a reducing agent, which can avoid the oxidation of manganese ions and ferrous ions, obtain high-purity sodium ferromanganese borate, and achieve uniform doping of ferromanganese; then
  • the prepared sodium ferromanganese borate is mixed with carbon source, vanadium source, sodium source and other components, and after grinding, spray drying and calcination, sodium vanadate and carbon can be coated on the surface of sodium ferromanganese borate at the same time.
  • sodium vanadate coated on the surface of the polyanionic sodium battery material that is, sodium manganese iron borate
  • sodium vanadate also has excellent It has the characteristics of excellent ionic conductivity and electronic conductivity, high capacity and good cycle performance.
  • the carbon coated on the surface of the polyanionic sodium battery material can further improve the electronic conductivity; thus making the prepared sodium ion battery cathode material have excellent electrochemical properties.
  • the preparation method of the sodium ion battery cathode material provided by the present invention can increase the voltage platform, improve the ion conductivity and electronic conductivity through manganese doping, sodium vanadate and carbon coating; and can appropriately increase the sodium ion
  • the primary particle size of the battery cathode material increases the compaction density and further improves its resistance to oxygen and moisture, so that the prepared sodium ion battery cathode material has the characteristics of high capacity and high energy density. Its energy density is similar to that of iron phosphate. Lithium materials are close to each other, and the cost is significantly lower than that of lithium iron phosphate materials.
  • the total raw materials, energy consumption, equipment depreciation and labor costs of the sodium ion battery cathode material of the present invention are approximately 39,500 yuan/ton, while the raw materials, energy consumption, equipment depreciation and labor costs of the lithium iron phosphate material are The total labor cost is about 132,000 yuan/ton.
  • the preparation cost of the sodium-ion battery cathode material of the present invention is significantly lower than that of lithium iron phosphate material.
  • step (A) calcination includes: in a nitrogen atmosphere, heating to 400-500°C and holding for 4-5 hours, then raising the temperature to 650-700°C and holding for 3-5 hours, and then cooling down. to ⁇ 120°C; preferably, the relative humidity of calcination is 3% to 5%.
  • step (A) calcination includes: heating to 400-500°C for 4-5 hours in a nitrogen atmosphere at a rate of 1-3°C/min, and then maintaining the temperature at 1-3°C/min. Raise the temperature to 650 ⁇ 700°C at a rate of 3°C/min and keep it for 3 ⁇ 5 hours, then cool down to ⁇ 120°C at a rate of 1 ⁇ 3°C/min and discharge the material.
  • step (A) the mixture of an aqueous solution of sodium borohydride and ferromanganese hydroxide is ground to obtain a first slurry; preferably, the concentration of the aqueous solution of sodium borohydride is 1 to 1.5 mol. /L.
  • step (A) the ratio of the sum of the moles of Fe and Mn in ferromanganese (II) hydroxide to the moles of Na in sodium borohydride is 0.97 to 1.02:1 ;
  • the particle size of the first slurry in step (A), is 200-300 nm; typically but not limiting, for example, in step (A), the particle size of the first slurry is 200nm, 220nm, 240nm, 260nm, 280nm or 300nm, etc.
  • step (A) the preparation method of ferric manganese (II) hydroxide includes the following steps:
  • Manganese salt, ferrous salt, complexing agent, sodium hydroxide, hydrazine hydrate, ammonia and titanyl sulfate react in the water phase to obtain ferric manganese hydroxide (II).
  • the present invention first prepares ferromanganese hydroxide with uniform coprecipitation of ferromanganese through co-precipitation, and then reacts with sodium borohydride to achieve uniform doping of ferromanganese and avoid the existence of a single rich source of sodium manganese borate in a certain place. accumulation, causing capacity fading.
  • the reaction temperature is 50-60°C, and the reaction time is 15-150 min.
  • the molar ratio of Mn in the manganese salt and Fe in the ferrous salt is 1:1.5 ⁇ 4; typical but not limiting, for example, manganese
  • the molar ratio of Mn in the salt to Fe in the ferrous salt is 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 or 1:4, etc.
  • the ratio of the sum of the moles of Mn in the manganese salt and Fe in the ferrous salt to the moles of Ti in titanium oxysulfate is 100: 0.1 ⁇ 0.2.
  • molar ratio of NH 3 ⁇ H 2 O in sodium hydroxide, hydrazine hydrate and ammonia water is 1:0.01 ⁇ 0.1:5.5 ⁇ 10.5:0.01 ⁇ 0.1:0.05 ⁇ 0.5.
  • the mass ratio of the sum of the masses of manganese salt, ferrous salt, complexing agent, sodium hydroxide, hydrazine hydrate, ammonia water and titanyl sulfate to water It is 10:1.5 ⁇ 3.
  • the ferrous salt includes ferrous sulfate, ferrous chloride and ferrous acetate.
  • the complexing agent includes at least one of ethylenediaminetetraacetic acid (EDTA), disodium ethylenediaminetetraacetate, sodium hexametaphosphate and triethanolamine.
  • the concentration of ammonia water is 5 to 8 mol/L.
  • the preparation method of ferromanganese hydroxide includes the following steps:
  • the mixed solution of manganese salt, ferrous salt, complexing agent, sodium hydroxide, hydrazine hydrate, ammonia, titanyl sulfate and water is slowly added to the reaction kettle.
  • the pH of the mixed solution is 9.5 to 10.
  • the temperature is controlled at 50 during the addition process. ⁇ 60°C. After the addition is completed, continue the reaction at 50-60°C for 15-30 minutes; during the reaction process, control the concentration of free ammonia in the mixed solution to 8-12g/L.
  • a reaction will occur. Ammonia water and metal ions precipitate to obtain ammonium radicals, which are not free ammonia. At the same time, part of the ammonia will also volatilize, so the amount of ammonia water added needs to be continuously adjusted to adjust the free ammonia in the solution.
  • the vanadium source in step (B), includes ammonium metavanadate.
  • the sodium source in step (B), includes at least one of sodium bicarbonate, sodium hydroxide, sodium acetate and sodium nitrate; preferably, the sodium source includes sodium bicarbonate.
  • the carbon source in step (B), includes nano-hydrophilic graphite and/or polyethylene glycol; preferably, the mass ratio of nano-hydrophilic graphite and polyethylene glycol is 1:5 ⁇ 10.
  • step (B) before calcination, the conductivity of the coating layer can be greatly improved by introducing an inorganic carbon source.
  • the carbon obtained by thermal decomposition of conventional organic carbon sources is amorphous carbon with a very low degree of graphitization and lower conductivity than graphitized carbon.
  • the present invention directly introduces inorganic carbon sources and adds polyethylene glycol to achieve dispersion.
  • polyethylene glycol will also thermally decompose to obtain carbon, realizing the combination of inorganic carbon source and organic carbon source, and the organic carbon source forms a A carbon network connects the inorganic carbon source to solve the problem of uneven coating of the inorganic carbon source in the coating layer.
  • step (B) the molar ratio of sodium in the first calcined material, vanadium in the vanadium source, and sodium in the sodium source is 1:0.02-0.03:0.06-0.09.
  • the mass ratio of the carbon source and the first calcined material is 3-10:100; preferably, the mass ratio of the carbon source and the first calcined material is 5-8: 100.
  • step (B) the ratio of the total mass of the first calcined material, carbon source, vanadium source and sodium source to the mass of water is 1:2-3.
  • step (B) calcination includes: raising the temperature to 720-750°C and holding it for 2-4 hours in a nitrogen atmosphere, and then lowering the temperature to ⁇ 80°C; preferably, in step (B) , Calcining includes: in a nitrogen atmosphere, heating to 720-750°C at a rate of 1-3°C and holding for 2-4 hours, and then cooling to ⁇ 80°C at a rate of 1-3°C.
  • the particle size of the second slurry is 100-200 nm.
  • the particle size of the second slurry after spray drying is 5 to 10 ⁇ m; preferably, a pressure spray dryer is used for spray drying.
  • pulverizing includes using a jet pulverizer; preferably, pulverizing until the particle size of the second slurry after spray drying is 0.5 to 2 ⁇ m; more preferably, pulverizing
  • the temperature is 120-150°C
  • the crushing pressure is 0.25-0.5MPa
  • the crushing includes crushing in a nitrogen atmosphere.
  • screening includes using an ultrasonic vibrating screen of 100 to 200 mesh.
  • step (B) removing iron includes using an electromagnetic iron remover to remove iron until the magnetic substance in the pulverized second slurry is ⁇ 1 ppm.
  • a sodium-ion battery cathode material is also provided, which is prepared by using the above-mentioned preparation method of a sodium-ion battery cathode material.
  • the primary particle size of the sodium ion battery cathode material is 150 to 250 nm.
  • the sodium ion battery cathode material of the present invention is constructed with layered oxide sodium vanadate and carbon as the surface and polyanionic sodium battery material as the core. Sodium vanadate and carbon are coated on the surface of the polyanionic sodium battery material to form a layer. The protective layer.
  • a sodium ion battery including the sodium ion battery cathode material as described above.
  • A Mix an aqueous solution of sodium borohydride with a concentration of 1.3 mol/L and ferromanganese hydroxide (II) and add it to a sand mill for sand grinding to obtain a first slurry with a particle size of 252 nm.
  • the first slurry After spray drying, in nitrogen with a relative humidity of 4.1%, first raise the temperature to 450°C at a rate of 3°C/min and keep it for 5 hours, then raise the temperature to 680°C at a rate of 2°C/min and keep it for 4 hours, and then keep it at 3°C for 4 hours. The temperature is lowered to 120°C at a rate of °C/min, and the first calcined material is discharged.
  • the ratio of the sum of the moles of Mn and Fe in ferromanganese hydroxide (II) to the moles of sodium borohydride is 1.01:1;
  • the preparation method of ferric manganese hydroxide (II) includes the following steps: mixing manganese sulfate, ferrous sulfate, EDTA, sodium hydroxide, ammonia water (concentration is 6 mol/L), hydrazine hydrate, titanyl sulfate and deionized water The liquid is added into the reaction kettle.
  • the molar ratio of NH 3 ⁇ H 2 O in manganese sulfate, ferrous sulfate, EDTA, sodium hydroxide, hydrazine hydrate and ammonia water is 1:2.52:0.05:7.58:0.04:0.18.
  • the concentration of free ammonia in the solution is controlled during the reaction process to be 10g/L; the reaction solution is filtered to obtain a filter cake, which is treated with 0.015 mol/ L is washed with hydrazine hydrate and then dried in a vacuum oven to obtain ferromanganese hydroxide (II).
  • the first calcined material, carbon source, ammonium metavanadate, sodium bicarbonate and water are mixed and then added to the sand mill for sand grinding to obtain a second slurry with a particle size of 183 nm.
  • the second slurry adopts a pressure type
  • the spray dryer performs spray drying to obtain a spray material with a particle size of 8.7 ⁇ m. In a nitrogen atmosphere, the spray material is first heated to 735°C at a rate of 3°C/min and kept for 3 hours, and then cooled to 80°C at a rate of 3°C/min.
  • the second calcined material is discharged to obtain the second calcined material; the second calcined material is pulverized at 145°C in a nitrogen atmosphere with a pressure of 0.35MPa until the particle size of the second calcined material is 1.2 ⁇ m; then a 150 mesh ultrasonic vibrating screen is used, and then Use an electromagnetic iron remover to remove iron until the magnetic substance in the second calcined material reaches 0.21 ppm, and then vacuum package it to obtain a sodium ion battery cathode material.
  • the carbon source is nanometer hydrophilic graphite and polyethylene glycol with a mass ratio of 1:7; the molar ratio of sodium in the first calcined material, vanadium in ammonium metavanadate and sodium bicarbonate is 1:0.025:0.08 ; The mass ratio of the carbon source to the first calcined material is 6:100, and the mass ratio of the total mass of the first calcined material, carbon source, ammonium metavanadate and sodium bicarbonate to water is 1:2.5.
  • A Mix an aqueous solution of sodium borohydride with a concentration of 1 mol/L and ferromanganese hydroxide (II) and add it to a sand mill for sand grinding to obtain a first slurry with a particle size of 200 nm.
  • the first slurry is After spray drying, in nitrogen with a relative humidity of 3%, first raise the temperature to 400°C at a rate of 1.5°C/min and keep it for 5 hours, then raise the temperature to 650°C at a rate of 1°C/min and keep it for 5 hours, and then keep it at 3°C for 5 hours. The temperature is lowered to 120°C at a rate of /min, and the first calcined material is discharged.
  • the ratio of the sum of the moles of Mn and Fe in ferromanganese hydroxide (II) to the moles of sodium borohydride is 0.97:1;
  • the preparation method of ferric manganese hydroxide (II) includes the following steps: adding manganese chloride, ferrous sulfate, EDTA, sodium hydroxide, ammonia water (concentration is 5 mol/L), hydrazine hydrate, titanyl sulfate and deionized water. The mixed solution is added to the reaction kettle.
  • the molar ratio of NH 3 ⁇ H 2 O in manganese chloride, ferrous sulfate, EDTA, sodium hydroxide, hydrazine hydrate and ammonia is 1:1.5:0.01:5.5:0.01:0.05.
  • Chlorine The ratio of the sum of the moles of Mn in manganese oxide and Fe in ferrous sulfate to the moles of Ti in titanyl sulfate is 100:0.1.
  • the addition time is 60 minutes.
  • the pH of the mixed solution during the addition is 9.6. Stir.
  • the speed is 600r/min and the temperature is 60°C.
  • the concentration of free ammonia in the reaction process control solution is 10g/L; the reaction liquid is filtered to obtain a filter cake, which is After washing with 0.01 mol/L hydrazine hydrate, it is dried in a vacuum oven to obtain ferric manganese hydroxide (II).
  • the first calcined material, carbon source, ammonium metavanadate, sodium bicarbonate and water are mixed and then added to the sand mill for sand grinding to obtain a second slurry with a particle size of 100 nm.
  • the second slurry adopts a pressure type
  • the spray dryer performs spray drying to obtain a spray material with a particle size of 5 ⁇ m; in a nitrogen atmosphere, the spray material is first heated to 720°C at a rate of 3°C/min and kept for 2 hours, and then cooled to 80°C at a rate of 3°C/min.
  • the second calcined material is discharged to obtain the second calcined material; the second calcined material is pulverized in a nitrogen atmosphere with a pressure of 0.35MPa at 145°C until the particle size of the second calcined material is 1.1 ⁇ m; then a 150 mesh ultrasonic vibrating screen is used, and then electromagnetic
  • the iron remover removes iron until the magnetic substance in the second calcined material reaches 0.3 ppm and then is vacuum packed to obtain the sodium ion battery cathode material.
  • the carbon source is nanometer hydrophilic graphite and polyethylene glycol with a mass ratio of 1:5; the molar ratio of sodium in the first calcined material, vanadium in ammonium metavanadate and sodium bicarbonate is 1:0.02:0.06 ; The mass ratio of the carbon source to the first calcined material is 3:100, and the mass ratio of the total mass of the first calcined material, carbon source, ammonium metavanadate and sodium bicarbonate to water is 1:2.
  • A Mix an aqueous solution of sodium borohydride with a concentration of 1.5 mol/L and ferromanganese hydroxide (II) and add it to a sand mill for sand grinding to obtain a first slurry with a particle size of 300 nm.
  • the first slurry After spray drying, in nitrogen with a relative humidity of 5%, first raise the temperature to 500°C at a rate of 3°C/min and keep it for 5 hours, then raise the temperature to a temperature of 700°C and keep it for 4 hours at a rate of 3°C/min, and then keep it at 1 The temperature is lowered to 120°C at a rate of °C/min, and the first calcined material is discharged.
  • the ratio of the sum of the moles of Mn and Fe in ferromanganese hydroxide (II) to the moles of sodium borohydride is 1.02:1;
  • the preparation method of ferric manganese hydroxide (II) includes the following steps: combining manganese acetate, ferrous chloride, triethanolamine, sodium hydroxide, ammonia (concentration is 8mol/L), hydrazine hydrate, titanyl sulfate and deionized water The mixed solution is added into the reaction kettle.
  • the molar ratio of manganese acetate, ferrous chloride, triethanolamine, sodium hydroxide, hydrazine hydrate and NH 3 ⁇ H 2 O in ammonia water is 1:4:0.1:10.5:0.1:0.5
  • the ratio of the sum of the moles of Mn in manganese chloride and Fe in ferrous sulfate to the moles of Ti in titanyl sulfate is 100:0.2
  • the addition time is 120min
  • the pH of the mixed solution during the addition is 9.9
  • the stirring speed is 550r/min
  • the temperature is 50°C
  • the concentration of free ammonia in the reaction process control solution is 10g/L
  • the reaction liquid is filtered to obtain a filter cake, filter The cake is washed with 0.015 mol/L hydrazine hydrate and then dried in a vacuum oven to obtain ferric manganese hydroxide (II).
  • the first calcined material, carbon source, ammonium metavanadate, sodium bicarbonate and water are mixed and then added to the sand mill for sand grinding to obtain a second slurry with a particle size of 200 nm.
  • the second slurry adopts a pressure type
  • the spray dryer performs spray drying to obtain a spray material with a particle size of 10 ⁇ m; in a nitrogen atmosphere, the spray material is first heated to 750°C at a rate of 3°C/min and kept for 3 hours, and then cooled to 80°C at a rate of 3°C/min.
  • Discharged material got the first The second calcined material; the second calcined material is pulverized in a nitrogen atmosphere with a pressure of 0.35MPa at 145°C until the particle size of the second calcined material is 1.3 ⁇ m; then a 150-mesh ultrasonic vibrating screen is used, and then an electromagnetic iron remover is used. Remove iron until the magnetic substance in the second calcined material is 0.2 ppm and then vacuum package to obtain a sodium ion battery cathode material.
  • the carbon source is nanometer hydrophilic graphite and polyethylene glycol with a mass ratio of 1:10; the molar ratio of sodium in the first calcined material, vanadium in ammonium metavanadate and sodium bicarbonate is 1:0.03:0.09 ; The mass ratio of the carbon source to the first calcined material is 10:100, and the mass ratio of the total mass of the first calcined material, carbon source, ammonium metavanadate and sodium bicarbonate to water is 1:3.
  • the preparation method of the sodium ion battery cathode material provided in this comparative example refers to Example 1. The only difference is that in step (B), ammonium metavanadate is not added.
  • the ferromanganese (II) hydroxide produced in the present invention has a spherical shape and is a flocculent agglomerate, with a large specific surface area, a small primary particle size, and high reactivity.
  • the first calcined material prepared in Example 1 was subjected to a scanning test, and the results are shown in Figure 2.
  • the properties of the first calcined material prepared in Example 1 were tested, and the results are shown in Table 2.
  • the compacted density is the density of the powder product under 3T pressure.
  • Example 3 The spray material prepared in Example 1 was subjected to a scanning test, and the results are shown in Figure 3.
  • the sodium ion battery cathode material prepared in Example 1 was subjected to a scanning test, and the results are shown in Figure 4.
  • the properties of the sodium ion battery cathode material prepared in Example 1 were tested, and the results are shown in Table 3.
  • the compacted density is the density of the powder product under 3T pressure.
  • the sodium ion battery cathode material prepared in Example 1 and the sodium ion battery cathode material prepared in Comparative Example 1 were respectively prepared by using carbon-coated aluminum foil as the current collector; at the same time, sodium hexafluorophosphate was used as the electrolyte and hard carbon was used as the negative electrode.
  • a 3Ah soft pack battery was prepared. At 25°C, cycle at 1C rate Ring performance test.
  • Figure 5 is a graph showing the relationship between the capacity retention rate and the number of cycles of the sodium ion battery cathode material prepared in Example 1.
  • Figure 6 is a charge-discharge curve of the sodium-ion battery cathode material prepared in Example 1, where A1 and A are the charge-discharge curves at a rate of 0.2C, and B1 and B are the charge-discharge curves at 1C. Then detect its DC resistance (DCR) at 50% SOC (50% capacity remaining), the discharge rate is 2C, and the battery is 3Ah. A is the battery made for the first time. Two parallel experiments were done, and D is Two parallel experiments were conducted on batteries made of the same materials for the second time, and the results are shown in Figure 7.
  • DCR DC resistance
  • the sodium-ion battery cathode material of the present invention has excellent cycle performance, with a capacity retention rate of ⁇ 95% for 500 cycles under 1C conditions. It can be seen from Figure 6 that the sodium ion battery cathode material of the present invention has a capacity of about 118 mAh/g at 1C, which is a relatively high capacity. As for the sodium-ion battery cathode material of Comparative Example 1, the capacity retention rate after 500 cycles under 1C conditions is only 91%, and the 1C discharge capacity is only 110.5mAh/g.
  • the DCR is all at 16m ⁇ , and the DCR is relatively low.
  • the sodium ion battery cathode material of the present invention has a relatively high compaction density of 2.37g/mL, and the expected electrode piece can reach more than 2.45g/mL after compaction. Moreover, the sodium ion battery cathode material of the present invention has good cycle performance, high capacity and high voltage platform. At the same time, according to calculations, the cost of the sodium ion battery cathode material of the present invention is only less than 30% of the cost of lithium iron phosphate. The cost performance is very excellent and can be applied to two-wheeled vehicles, electric buses, low-endurance electric vehicles and other fields.

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Abstract

涉及钠离子电池技术领域，尤其是涉及一种钠离子电池正极材料及其制备方法和应用。所述钠离子电池正极材料的制备方法，包括如下步骤：(A)硼氢化钠和氢氧化锰铁的混合物研磨后得到第一浆料，所述第一浆料经喷雾干燥和煅烧后得到第一煅烧料；(B)所述第一煅烧料、碳源、钒源、碳酸氢钠和水的混合物研磨后得到第二浆料，所述第二浆料依次经过喷雾干燥、煅烧、粉碎、筛分和除铁后得到所述钠离子电池正极材料。该方法步骤简单、成本低、制得的钠离子电池正极材料具有导电性好、容量高和能量密度高等特点。

Description

钠离子电池正极材料及其制备方法和应用
本申请要求于2022年07月29日提交中国专利局、申请号为202210905141.2、发明名称为“一种钠离子电池正极材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及钠离子电池技术领域，尤其是涉及一种钠离子电池正极材料及其制备方法和应用。
背景技术
汽车产能的爆发让锂资源价格上涨，锂电池除了锂之外，还使用另一种稀有金属-钴(Co)。研究显示，利用现行技术生产1辆纯电动汽车(EV)，大约要使用20kg的锂和大约40kg的Co。锂和钴这种稀缺能源不可避免的会面临资源减少和价格上涨。而钠作为仅次于锂的第2轻的金属元素，丰度高达2.3％～2.8％，比锂高4～5个数量级，且与锂有着相似的物理化学性质，因此，钠离子电池得到广泛关注。
早在20世纪七八十年代，有着“后锂电池”之称的钠离子电池就已经被提出，与锂离子电池几乎同时起步，但随着锂离子电池的成功商业化，钠离子电池研究逐渐被淡化。当时只是简单的将锂离子电池上成功应用的电极材料套用到钠离子电池上，没有考虑钠离子电池与锂离子电池对材料晶格结构要求的区别，导致钠离子电池的效果较差。近年来，随着人们逐渐认识到锂离子电池大规模应用带来的锂资源紧张，以及充分从钠离子电池的特殊性来设计电极材料，进而取得了较好的效果，使钠离子电池重新成为研究热点。
目前，层状氧化物钠电池材料，虽然具有能量密度高的优点，但是其循环性能很差。普鲁士蓝结构的钠电池材料，能量密度还是偏低，且结构不稳定，存在有毒有害的原材料。聚阴离子钠电池材料具有结构稳定、循环寿命长等优点，但是一般其容量比较低，能量密度低。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种钠离子电池正极材料的制备方法，该方法步骤简单、成本低、制得的钠离子电池正极材料具有导电性好、容量高、能量 密度高等特点。
本发明的第二目的在于提供一种钠离子电池正极材料，采用如上所述的钠离子电池正极材料的制备方法制备得到
本发明的第三目的在于提供一种钠离子电池，包括如上所述的钠离子电池正极材料。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种钠离子电池正极材料的制备方法，包括如下步骤：
(A)硼氢化钠和氢氧化锰铁的混合物研磨后得到第一浆料，所述第一浆料经喷雾干燥和煅烧后得到第一煅烧料；
(B)所述第一煅烧料、碳源、钒源、碳酸氢钠和水的混合物研磨后得到第二浆料，所述第二浆料依次经过喷雾干燥、煅烧、粉碎、筛分和除铁后得到所述钠离子电池正极材料。
本发明还提供了一种钠离子电池正极材料，采用如上所述的钠离子电池正极材料的制备方法制备得到。
本发明还提供了一种钠离子电池，包括如上所述的钠离子电池正极材料。
与现有技术相比，本发明的有益效果为：
本发明提供的钠离子电池正极材料的制备方法，通过金属离子的掺杂、钒酸钠和碳的包裹，可以大大提高离子导电性和电子导电性，且可以适当的增大钠离子电池正极材料的一次粒径，从而提高压实密度、提高其对氧气和水分的抵御程度，从而使制得的钠离子电池正极材料的能量密度接近磷酸铁锂材料，可达170wh/kg，且成本也比磷酸铁锂材料低很多。
采用本发明的钠离子电池正极材料的制备方法制得的钠离子电池正极材料，以聚阴离子钠电池材料，即硼酸锰铁钠为核心，钒酸钠和碳同时包覆在聚阴离子钠电池材料的表面，从而形成一层保护层，其中，钒酸钠可以保护内核的聚阴离子电池材料，避免其接触氧气和水分，并且有利于提高离子导电性和电子导电性、容量和循环性能，碳可以进一步提升了电子导电性，从而使钠离子电池正极材料具有优异的电化学性能。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将 对具体实施方式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，下面描述中的附图是本发明的一些实施方式，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制得的氢氧化锰铁(Ⅱ)的SEM图。
图2为本发明实施例1制得的第一煅烧料的SEM图。
图3为本发明实施例1制得的喷雾料的SEM图。
图4为本发明实施例1制得的钠离子电池正极材料的SEM图。
图5为本发明实施例1制得的钠离子电池正极材料的容量保持率与循环次数的关系图。
图6为本发明实施例1制得的钠离子电池正极材料的充放电曲线图。
图7为本发明实施例1制得的钠离子电池正极材料在容量剩余50％时的直流电阻图。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明实施例的一种钠离子电池正极材料及其制备方法和应用进行具体说明。
在本发明的一些实施方式中提供了钠离子电池正极材料的制备方法，包括如下步骤：
(A)硼氢化钠和氢氧化锰铁的混合物研磨后得到第一浆料，第一浆料经喷雾干燥和煅烧后得到第一煅烧料；
(B)第一煅烧料、碳源、钒源、钠源和水的混合物研磨后得到第二浆料，第二浆料依次经过喷雾干燥、煅烧、粉碎、筛分和除铁后得到钠离子电池正极材料。
本发明提供的钠离子电池正极材料的制备方法，通过采用硼氢化钠和氢氧化锰铁(Ⅱ)制得第一煅烧料，即硼酸锰铁钠(Na(Fe,Mn)BO3)；以硼氢化钠作为硼源和钠源，且硼氢化钠为还原剂，可以避免亚锰离子和亚铁离子被氧化，可以得到高纯度的硼酸锰铁钠，并实现锰铁的均匀掺杂；然后制得的硼酸锰铁钠通过与碳源、钒源和钠源等组分混合后，经研磨、喷雾干燥、煅烧后可实现钒酸钠和碳同时包覆在硼酸锰铁钠的表面，从而形成一层保护层；包覆在聚阴离子钠电池材料，即硼酸锰铁钠表面的钒酸钠，可以保护内核的聚阴离子钠电池材料，避免其接触氧气和水分，同时钒酸钠也具有优良的离子导电性和电子导电性、容量高和循环性能好的特点，包覆在聚阴离子钠电池材料表面的碳，可以进一步提升了电子导电性；从而使制得的钠离子电池正极材料具有优异的电化学性能。
本发明提供的钠离子电池正极材料的制备方法，通过锰的掺杂、钒酸钠和碳的包覆，可以提高电压平台、提高离子导电性和电子导电性；且可以适当的增大钠离子电池正极材料的一次粒径，从而提高压实密度，进一步提高其对氧气和水分的抵御程度，使制得的钠离子电池正极材料具有高容量、高能量密度的特点，其能量密度与磷酸铁锂材料相接近，且成本比磷酸铁锂材料的成本大幅度降低。
按照目前各个原材料的价格来计算，本发明钠离子电池正极材料的原材料、能耗、设备折旧和人工成本总计约为3.95万元/吨，而磷酸铁锂材料的原材料、能耗、设备折旧和人工成本总计约为13.2万元/吨，本发明的钠离子电池正极材料的制备成本明显低于磷酸铁锂材料。
在本发明的一些实施方式中，步骤(A)中，煅烧包括：在氮气气氛中，升温至400～500℃保温处理4～5h，再升温至650～700℃保温处理3～5h，再降温至≤120℃；优选地，煅烧的相对湿度为3％～5％。
在本发明的一些具体的实施方式中，步骤(A)中，煅烧包括：在氮气气氛中，以1～3℃/min的速率升温至400～500℃保温处理4～5h，再以1～3℃/min的速率升温至650～700℃保温处理3～5h，再以1～3℃/min的速率降温至≤120℃，出料。
本发明的钠离子电池正极材料的制备方法中，上述煅烧过程中，将具有一 定湿度的氮气作为保护气体和反应剂，可以与硼氢化钠反应，得到还原性气体，从而保护亚锰离子和亚铁离子不被氧化。
在本发明的一些实施方式中，步骤(A)中，硼氢化钠的水溶液和氢氧化锰铁的混合物研磨后得到第一浆料；优选地，硼氢化钠的水溶液的浓度为1～1.5mol/L。
在本发明的一些实施方式中，步骤(A)中，氢氧化锰铁(Ⅱ)中的Fe和Mn的摩尔数之和与硼氢化钠中的Na的摩尔数的比为0.97～1.02：1；典型但非限制性的，例如，氢氧化锰铁(Ⅱ)中的Fe和Mn的摩尔数之和与硼氢化钠中的Na的摩尔数的比为0.97：1、0.98：1、0.99：1、1：1、1.01：1或者1.02：1等等。
在本发明的一些实施方式中，步骤(A)中，第一浆料的粒径为200～300nm；典型但非限制性的，例如，步骤(A)中，第一浆料的粒径为200nm、220nm、240nm、260nm、280nm或者300nm等等。
在本发明的一些实施方式中，步骤(A)中，氢氧化锰铁(Ⅱ)的制备方法，包括如下步骤：
锰盐、亚铁盐、络合剂、氢氧化钠、水合肼、氨水和硫酸氧钛于水相中反应得到氢氧化锰铁(Ⅱ)。
本发明通过共沉淀先制备得到锰铁均匀共沉淀的氢氧化锰铁，然后再与硼氢化钠反应，可以实现锰铁的均匀掺杂，避免在某一地方，存在单独的硼酸锰钠的富集物，从而造成容量衰减。
在本发明的一些实施方式中，氢氧化锰铁(Ⅱ)的制备方法中，反应的温度为50～60℃，反应的时间为15～150min。
在本发明的一些实施方式中，氢氧化锰铁的制备方法中，锰盐中的Mn和亚铁盐中的Fe的摩尔比为1：1.5～4；典型但非限制性的，例如，锰盐中的Mn和亚铁盐中的Fe的摩尔比为1：1.5、1：2、1：2.5、1：3、1：3.5或者1：4等等。
在本发明的一些实施方式中，氢氧化锰铁的制备方法中，锰盐中的Mn和亚铁盐中的Fe的摩尔数之和与硫酸氧钛中的Ti的摩尔数的比为100：0.1～0.2。
在本发明的一些实施方式中，氢氧化锰铁的制备方法中，锰盐、络合剂、 氢氧化钠、水合肼和氨水中的NH3·H2O的摩尔比为1：0.01～0.1：5.5～10.5：0.01～0.1：0.05～0.5。
在本发明的一些实施方式中，氢氧化锰铁的制备方法中，锰盐、亚铁盐、络合剂、氢氧化钠、水合肼、氨水和硫酸氧钛的质量之和与水的质量比为10：1.5～3。
在本发明的一些实施方式中，氢氧化锰铁的制备方法中，硫酸锰、氯化锰和醋酸锰中的至少一种；亚铁盐包括硫酸亚铁、氯化亚铁和醋酸亚铁中的至少一种；络合剂包括乙二胺四乙酸(EDTA)、乙二胺四乙酸二钠、六偏磷酸钠和三乙醇胺中的至少一种。
在本发明的一些具体的实施方式中，氢氧化锰铁的制备方法中，氨水的浓度为5～8mol/L。
在本发明的一些具体的实施方式中，氢氧化锰铁的制备方法，包括如下步骤：
锰盐、亚铁盐、络合剂、氢氧化钠、水合肼、氨水、硫酸氧钛和水的混合溶液缓慢加入反应釜中，混合溶液的pH为9.5～10，加入过程中控制温度为50～60℃，加入完成后，继续在50～60℃条件下反应15～30min；反应过程中控制混合溶液中的游离氨的浓度为8～12g/L。在反应过程中，会发生反应，氨水与金属离子沉淀，得到铵根，不属于游离氨，同时部分氨也会挥发出来，所以需要不断调节加入氨水的量，来调节溶液中的游离氨。
在本发明的一些实施方式中，步骤(B)中，钒源包括偏钒酸铵。
在本发明的一些实施方式中，步骤(B)中，钠源包括碳酸氢钠、氢氧化钠、醋酸钠和硝酸钠中的至少一种；优选地，钠源包括碳酸氢钠。
在本发明的一些实施方式中，步骤(B)中，碳源包括纳米亲水石墨和/或聚乙二醇；优选地，纳米亲水石墨和聚乙二醇的质量比为1：5～10。
本发明提供的钠离子电池正极材料的制备方法，步骤(B)中，煅烧前，通过引入无机碳源，可以大大提高包覆层的导电性。常规的有机碳源热分解得到的碳，为无定型的碳，石墨化程度很低，导电性低于石墨化的碳，而本发明直接引入无机碳源，同时加入聚乙二醇来实现分散，同时在二次煅烧过程，聚乙二醇也会热分解得到碳，实现无机碳源和有机碳源的复合，有机碳源形成一 个碳网，将无机碳源连接住，从而解决包覆层中无机碳源包覆不均匀的问题。
在本发明的一些实施方式中，步骤(B)中，第一煅烧料中的钠、钒源中的钒和所述钠源中的钠的摩尔比为1：0.02～0.03：0.06～0.09。
在本发明的一些实施方式中，步骤(B)中，碳源和第一煅烧料的质量比为3～10：100；优选地，碳源和第一煅烧料的质量比为5～8：100。
在本发明的一些实施方式中，步骤(B)中，第一煅烧料、碳源、钒源和钠源的总质量与水的质量的比为1：2～3。
在本发明的一些实施方式中，步骤(B)中，煅烧包括：在氮气气氛中，升温至720～750℃保温处理2～4h，再降温至≤80℃；优选地，步骤(B)中，煅烧包括：在氮气气氛中，以1～3℃的速率升温至720～750℃保温处理2～4h，再以1～3℃的速率降温至≤80℃。
在本发明的一些实施方式中，步骤(B)中，第二浆料的粒径为100～200nm。
在本发明的一些实施方式中，步骤(B)中，喷雾干燥后的第二浆料的粒径5～10μm；优选地，喷雾干燥采用压力式喷雾干燥机。
在本发明的一些实施方式中，步骤(B)中，粉碎包括采用气流粉碎机粉碎；优选地，粉碎至喷雾干燥后的第二浆料的粒径为0.5～2μm；更优选地，粉碎的温度为120～150℃，粉碎的压力为0.25～0.5MPa，粉碎包括在氮气气氛中进行粉碎。
在本发明的一些实施方式中，步骤(B)中，筛分包括采用100～200目超声波振动筛。
在本发明的一些实施方式中，步骤(B)中，除铁包括采用电磁除铁器进行除铁至粉碎后的第二浆料中磁性物质≤1ppm。
在本发明的一些实施方式中还提供了一种钠离子电池正极材料，采用如上所述的钠离子电池正极材料的制备方法制备得到。
在本发明的一些实施方式中，钠离子电池正极材料的一次粒径为150～250nm。
本发明的钠离子电池正极材料，构建了以层状氧化物钒酸钠和碳为表面，以聚阴离子钠电池材料为核心，钒酸钠和碳包覆在聚阴离子钠电池材料表面形成一层保护层。
在本发明的一些实施方式中还提供了一种钠离子电池，包括如上所述的钠离子电池正极材料。
实施例1
本实施例提供的钠离子电池正极材料的制备方法，包括如下步骤：
(A)将浓度为1.3mol/L的硼氢化钠的水溶液和氢氧化锰铁(Ⅱ)混合后加入到砂磨机内进行砂磨得到粒径为252nm的第一浆料，第一浆料进行喷雾干燥后，在相对湿度为4.1％的氮气中，先以3℃/min的速率升温至450℃保温5h，然后以2℃/min的速率升温至温度为680℃保温4h，再以3℃/min的速率降温至120℃，出料得到第一煅烧料。
其中，氢氧化锰铁(Ⅱ)中的Mn和Fe的摩尔数之和与硼氢化钠的摩尔数的比为1.01：1；
氢氧化锰铁(Ⅱ)的制备方法，包括如下步骤：将硫酸锰、硫酸亚铁、EDTA、氢氧化钠、氨水(浓度为6mol/L)、水合肼、硫酸氧钛和去离子水的混合液加入到反应釜内，硫酸锰、硫酸亚铁、EDTA、氢氧化钠、水合肼和氨水中的NH3·H2O摩尔比为1：2.52：0.05：7.58：0.04：0.18，硫酸锰中的Mn和硫酸亚铁中的Fe的摩尔数之和与硫酸氧钛中的Ti的摩尔数的比为100：0.2，加入时间为95min，加入过程中混合溶液的pH为9.76，搅拌速度为500r/min，温度为55℃，加入完成后继续在55℃反应25min得到反应液，反应过程控制溶液中的游离氨的浓度为10g/L；反应液过滤后得到滤饼，滤饼经0.015mol/L的水合肼洗涤后放入真空烘箱烘干，得到氢氧化锰铁(Ⅱ)。
(B)第一煅烧料、碳源、偏钒酸铵、碳酸氢钠和水混合后加入到砂磨机内进行砂磨得到粒径为183nm的第二浆料，第二浆料采用压力式喷雾干燥机进行喷雾干燥得到粒径为8.7μm的喷雾料；喷雾料在氮气气氛中，先以3℃/min的速率升温至735℃保温3h，然后以3℃/min的速率降温至80℃，出料得到第二煅烧料；第二煅烧料在压力为0.35MPa的氮气气氛中，145℃下进行粉碎，直至第二煅烧料的粒径为1.2μm；然后采用150目超声波振动筛，再采用电磁除铁器进行除铁至第二煅烧料中磁性物质为0.21ppm后真空包装，得到钠离子电池正极材料。
其中，碳源为质量比为1：7的纳米亲水石墨和聚乙二醇；第一煅烧料中的钠、偏钒酸铵中的钒和碳酸氢钠的摩尔比为1：0.025：0.08；碳源与第一煅烧料的质量比为6：100，第一煅烧料、碳源、偏钒酸铵和碳酸氢钠总质量与水的质量比为1：2.5。
实施例2
本实施例的钠离子电池正极材料的制备方法，其包括如下步骤：
(A)将浓度为1mol/L的硼氢化钠的水溶液和氢氧化锰铁(Ⅱ)混合后加入到砂磨机内进行砂磨得到粒径为200nm的第一浆料，第一浆料进行喷雾干燥后，在相对湿度为3％的氮气中，先以1.5℃/min的速率升温至400℃保温5h，然后以1℃/min的速率升温至温度为650℃保温5h，再以3℃/min的速率降温至120℃，出料得到第一煅烧料。
其中，氢氧化锰铁(Ⅱ)中的Mn和Fe的摩尔数之和与硼氢化钠的摩尔数的比为0.97：1；
氢氧化锰铁(Ⅱ)的制备方法，包括如下步骤：将氯化锰、硫酸亚铁、EDTA、氢氧化钠、氨水(浓度为5mol/L)、水合肼、硫酸氧钛和去离子水的混合液加入到反应釜内，氯化锰、硫酸亚铁、EDTA、氢氧化钠、水合肼和氨水中的NH3·H2O摩尔比为1：1.5：0.01：5.5：0.01：0.05，氯化锰中的Mn和硫酸亚铁中的Fe的摩尔数之和与硫酸氧钛中的Ti的摩尔数的比为100：0.1，加入时间为60min，加入过程中混合溶液的pH为9.6，搅拌速度为600r/min，温度为60℃，加入完成后继续在60℃反应30min得到反应液，反应过程控制溶液中的游离氨的浓度为10g/L；反应液过滤后得到滤饼，滤饼经0.01mol/L的水合肼洗涤后放入真空烘箱烘干，得到氢氧化锰铁(Ⅱ)。
(B)第一煅烧料、碳源、偏钒酸铵、碳酸氢钠和水混合后加入到砂磨机内进行砂磨得到粒径为100nm的第二浆料，第二浆料采用压力式喷雾干燥机进行喷雾干燥得到粒径为5μm的喷雾料；喷雾料在氮气气氛中，先以3℃/min的速率升温至720℃保温2h，然后以3℃/min的速率降温至80℃，出料得到第二煅烧料；第二煅烧料在压力为0.35MPa的氮气气氛中，145℃下进行粉碎，直至第二煅烧料的粒径为1.1μm；然后采用150目超声波振动筛，再采用电磁 除铁器进行除铁至第二煅烧料中磁性物质为0.3ppm后真空包装，得到钠离子电池正极材料。
其中，碳源为质量比为1：5的纳米亲水石墨和聚乙二醇；第一煅烧料中的钠、偏钒酸铵中的钒和碳酸氢钠的摩尔比为1：0.02：0.06；碳源与第一煅烧料的质量比为3：100，第一煅烧料、碳源、偏钒酸铵和碳酸氢钠总质量与水的质量比为1：2。
实施例3
本实施例的一种钠离子电池正极材料的制备方法，包括如下步骤：
(A)将浓度为1.5mol/L的硼氢化钠的水溶液和氢氧化锰铁(Ⅱ)混合后加入到砂磨机内进行砂磨得到粒径为300nm的第一浆料，第一浆料进行喷雾干燥后，在相对湿度为5％的氮气中，先以3℃/min的速率升温至500℃保温5h，然后以3℃/min的速率升温至温度为700℃保温4h，再以1℃/min的速率降温至120℃，出料得到第一煅烧料。
其中，氢氧化锰铁(Ⅱ)中的Mn和Fe的摩尔数之和与硼氢化钠的摩尔数的比为1.02：1；
氢氧化锰铁(Ⅱ)的制备方法，包括如下步骤：将醋酸锰、氯化亚铁、三乙醇胺、氢氧化钠、氨水(浓度为8mol/L)、水合肼、硫酸氧钛和去离子水的混合液加入到反应釜内，醋酸锰、氯化亚铁、三乙醇胺、氢氧化钠、水合肼和氨水中的NH3·H2O摩尔比为1：4：0.1：10.5：0.1：0.5，氯化锰中的Mn和硫酸亚铁中的Fe的摩尔数之和与硫酸氧钛中的Ti的摩尔数的比为100：0.2，加入时间为120min，加入过程中混合溶液的pH为9.9，搅拌速度为550r/min，温度为50℃，加入完成后继续在50℃反应25min得到反应液，反应过程控制溶液中的游离氨的浓度为10g/L；反应液过滤后得到滤饼，滤饼经0.015mol/L的水合肼洗涤后放入真空烘箱烘干，得到氢氧化锰铁(Ⅱ)。
(B)第一煅烧料、碳源、偏钒酸铵、碳酸氢钠和水混合后加入到砂磨机内进行砂磨得到粒径为200nm的第二浆料，第二浆料采用压力式喷雾干燥机进行喷雾干燥得到粒径为10μm的喷雾料；喷雾料在氮气气氛中，先以3℃/min的速率升温至750℃保温3h，然后以3℃/min的速率降温至80℃，出料得到第 二煅烧料；第二煅烧料在压力为0.35MPa的氮气气氛中，145℃下进行粉碎，直至第二煅烧料的粒径为1.3μm；然后采用150目超声波振动筛，再采用电磁除铁器进行除铁至第二煅烧料中磁性物质为0.2ppm后真空包装，得到钠离子电池正极材料。
其中，碳源为质量比为1：10的纳米亲水石墨和聚乙二醇；第一煅烧料中的钠、偏钒酸铵中的钒和碳酸氢钠的摩尔比为1：0.03：0.09；碳源与第一煅烧料的质量比为10：100，第一煅烧料、碳源、偏钒酸铵和碳酸氢钠总质量与水的质量比为1：3。
对比例1
本对比例提供的钠离子电池正极材料的制备方法参考实施例1，不同之处仅在于，步骤(B)中，未添加偏钒酸铵。
试验例1
对实施例1制得的氢氧化锰铁(Ⅱ)进行扫描测试，其结果如图1所示。
从图1可知，本发明制得的氢氧化锰铁(Ⅱ)形貌为类球形，且为絮状团聚体，比表面积大，一次粒径小，反应活性高。
对实施例1制得的氢氧化锰铁(Ⅱ)的性质进行测试，其结果如表1所示。
表1
试验例2
对实施例1制得的第一煅烧料进行扫描测试，其结果如图2所示。对实施例1制得的第一煅烧料的性质进行测试，其结果如表2所示。压实密度为3T压力下粉末产品的密度。
表2
试验例3
对实施例1制得的喷雾料进行扫描测试，其结果如图3所示。对实施例1制得的钠离子电池正极材料进行扫描测试，其结果如图4所示。对实施例1制得的钠离子电池正极材料的性质进行测试，其结果如表3所示。压实密度为3T压力下粉末产品的密度。
表3
分别将实施例1制得的钠离子电池正极材料和对比例1的钠离子电池正极材料，采用涂碳铝箔为集流体制备正极材料；同时采用六氟磷酸钠为电解液，硬碳为负极，制备得到3Ah的软包电池。在25℃下，采用1C倍率下进行循 环性能测试。图5为实施例1的制得的钠离子电池正极材料的容量保持率与循环次数的关系图。图6为实施例1制得的钠离子电池正极材料的充放电曲线图，其中A1和A为0.2C倍率下的充放电曲线，B1和B是1C下的充放电曲线。然后检测其在50％SOC(容量剩余50％时)的直流电阻(DCR)，放电倍率为2C，电池为3Ah，其中A为第一次做成的电池，做的两个平行实验，D为相同的材料，第二次做成的电池，做的两个平行实验，其结果如图7所示。
从图5可以看出，本发明的钠离子电池正极材料的循环性能比较优异，1C条件下500周循环的容量保持率≥95％。从图6可以看出，本发明的钠离子电池正极材料，1C的容量118mAh/g左右，容量较高。而对比例1的钠离子电池正极材料，1C条件下500周循环的容量保持率仅为91％，1C放电容量仅为110.5mAh/g。
从图7可知，DCR均在16mΩ，DCR比较低。
从表3和图5-7可以看到，本发明的钠离子电池正极材料，压实密度较高，为2.37g/mL，预期的极片使用压实可以达到2.45g/mL以上。且本发明的钠离子电池正极材料的循环性能好，容量高，电压平台高。同时根据计算，本发明的钠离子电池正极材料的成本仅仅为磷酸铁锂成本的30％以下，性价比非常优异，可以适用于两轮车、电动大巴、低续航电动车等领域。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种钠离子电池正极材料的制备方法，其特征在于，包括如下步骤：
    (A)硼氢化钠和氢氧化锰铁的混合物研磨后得到第一浆料，所述第一浆料经喷雾干燥和煅烧后得到第一煅烧料；
    (B)所述第一煅烧料、碳源、钒源、钠源和水的混合物研磨后得到第二浆料，所述第二浆料依次经过喷雾干燥、煅烧、粉碎、筛分和除铁后得到所述钠离子电池正极材料。
  2. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(A)中，所述煅烧包括：在氮气气氛中，升温至400～500℃保温处理4～5h，再升温至650～700℃保温处理3～5h，再降温至≤120℃；
    优选地，所述煅烧的相对湿度为3％～5％；
    优选地，所述煅烧包括：在氮气气氛中，以1～3℃/min的速率升温至400～500℃保温处理4～5h，再以1～3℃/min的速率升温至650～700℃保温处理3～5h，再以1～3℃/min的速率降温至≤120℃，出料。
  3. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(A)中，所述氢氧化锰铁中的Fe和Mn的摩尔数之和与所述硼氢化钠中的Na的摩尔数的比为0.97～1.02：1；
    优选地，所述第一浆料的粒径为200～300nm。
  4. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(A)中，所述氢氧化锰铁的制备方法，包括如下步骤：
    锰盐、亚铁盐、络合剂、氢氧化钠、水合肼、氨水和硫酸氧钛于水相中反应得到所述氢氧化锰铁；
    优选地，所述反应的温度为50～60℃，所述反应的时间为15～150min。
  5. 根据权利要求4所述的钠离子电池正极材料的制备方法，其特征在于，所述锰盐中的Mn和所述亚铁盐中的Fe的摩尔比为1：1.5～4；
    优选地，所述锰盐中的Mn和所述亚铁盐中的Fe的摩尔数之和与所述硫酸氧钛中的Ti的摩尔数的比为100：0.1～0.2；
    优选地，所述锰盐、所述络合剂、所述氢氧化钠、所述水合肼和所述氨水 中的NH3·H2O的摩尔比为1：0.01～0.1：5.5～10.5：0.01～0.1：0.05～0.5；
    优选地，所述锰盐包括硫酸锰、氯化锰和醋酸锰中的至少一种；
    优选地，所述亚铁盐包括硫酸亚铁、氯化亚铁和醋酸亚铁中的至少一种；
    优选地，所述络合剂包括乙二胺四乙酸、乙二胺四乙酸二钠、六偏磷酸钠和三乙醇胺中的至少一种。
  6. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(B)中，所述钒源包括偏钒酸铵；
    优选地，所述钠源包括碳酸氢钠、氢氧化钠、醋酸钠和硝酸钠中的至少一种；
    优选地，所述碳源包括纳米亲水石墨和/或聚乙二醇；
    优选地，所述纳米亲水石墨和所述聚乙二醇的质量比为1：5～10。
  7. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(B)中，所述第一煅烧料中的钠、所述钒源中的钒和所述钠源中的钠的摩尔比为1：0.02～0.03：0.06～0.09；
    优选地，所述碳源和所述第一煅烧料的质量比为3～10：100；
    优选地，所述第一煅烧料、所述碳源、所述钒源和所述钠源的总质量与所述水的质量的比为1：2～3。
  8. 根据权利要求1所述的钠离子电池正极材料的制备方法，其特征在于，步骤(B)中，所述煅烧包括：在氮气气氛中，升温至720～750℃保温处理2～4h，再降温至≤80℃；
    优选地，所述煅烧包括：在氮气气氛中，以1～3℃的速率升温至720～750℃保温处理2～4h，再以1～3℃的速率降温至≤80℃；
    优选地，所述第二浆料的粒径为100～200nm；
    优选地，所述喷雾干燥后的第二浆料的粒径5～10μm。
  9. 一种钠离子电池正极材料，其特征在于，采用权利要求1～8任一项所述的钠离子电池正极材料的制备方法制备得到。
  10. 一种钠离子电池，其特征在于，包括权利要求9所述的钠离子电池正极材料。
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