WO2023137859A1 - 一种钠离子电池正极活性物质及其制备方法、应用 - Google Patents

一种钠离子电池正极活性物质及其制备方法、应用 Download PDF

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WO2023137859A1
WO2023137859A1 PCT/CN2022/082410 CN2022082410W WO2023137859A1 WO 2023137859 A1 WO2023137859 A1 WO 2023137859A1 CN 2022082410 W CN2022082410 W CN 2022082410W WO 2023137859 A1 WO2023137859 A1 WO 2023137859A1
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positive electrode
ion battery
electrode active
sodium ion
active material
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PCT/CN2022/082410
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English (en)
French (fr)
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龚黎明
钟欢
黄杰
蒋文
陈亮
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江苏翔鹰新能源科技有限公司
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Priority to KR1020237026214A priority Critical patent/KR20230128339A/ko
Priority to JP2023545953A priority patent/JP2024507080A/ja
Priority to US18/277,660 priority patent/US20240234711A9/en
Priority to EP22919289.3A priority patent/EP4266419A1/en
Publication of WO2023137859A1 publication Critical patent/WO2023137859A1/zh

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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • 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
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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
    • 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
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    • 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 belongs to the field of sodium ion batteries, and in particular relates to a positive electrode active material of a sodium ion battery and a preparation method and application thereof.
  • Lithium-ion batteries have been widely used in electric vehicles, medium and large energy storage power stations, electric two-wheeled vehicles, electric tools, portable electronic devices and other fields.
  • the problem of structural shortage of lithium resources has become prominent, leading to a sharp rise in the price of lithium salts and a sharp increase in the cost of lithium-ion batteries.
  • Na-ion batteries and lithium-ion batteries have similar electrochemical properties, and sodium-ion batteries are rich in resources and low in cost.
  • sodium-ion batteries have become a hot development direction and are expected to be widely used in the fields of electric two-wheelers and medium and large energy storage power stations.
  • the positive electrode active materials of sodium ion batteries that have shown potential application prospects include three types of systems: Prussian blue, layered oxides, and polyanions.
  • the layered oxide system with O3 structure is similar to the ternary positive electrode active material in lithium-ion batteries. It has the advantages of high capacity and high compaction density. It is regarded as the most potential positive electrode material and is adopted by domestic and foreign sodium-ion battery companies.
  • Chinese patent CN109817970A discloses a preparation method of a single crystal sodium ion battery electrode material. After mixing and reacting a mixed aqueous solution of iron salt, manganese salt and M salt, a precipitant, a complexing agent and a dispersant, the solid obtained is a battery electrode material precursor; the precursor and sodium salt are mixed, sintered, and cooled to obtain a single crystal sodium ion battery electrode material; wherein the dispersant is ammonium polyacrylate.
  • the above-mentioned specific ammonium polyacrylate dispersant is not used, the crystal morphology of the crystal grains is not obvious, and micron-sized single crystals cannot be formed, and the discharge capacity and capacity retention rate of the corresponding battery electrode materials are also low.
  • Layered oxide cathode active materials exhibit excellent electrochemical performance, but there are many structural phase changes during charging and discharging, poor air storage performance, high surface alkalinity, and side reactions with electrolytes, which greatly restrict the large-scale commercial application of such active materials.
  • the object of the present invention is to address the shortcomings and deficiencies of the prior art, and provide a positive electrode active material for a sodium ion battery, which can ensure the excellent gram capacity performance of the sodium ion battery, improve cycle performance at high temperatures, and simultaneously form a stable single crystal structure with low surface alkalinity.
  • a positive electrode active material for a sodium ion battery the chemical formula of the positive electrode active material is Na x Ni y Fez Mn g M h A m O 2 , wherein M is a combination of one or more selected from Ti, Al, Mg, Ca, Zr, Y, Zn, Nb, and W, A is a combination of one or more selected from B, P, and C, 0.80 ⁇ x ⁇ 1.40, 0.05 ⁇ y ⁇ 0.95, 0.05 ⁇ z ⁇ 0.95, 0.05 ⁇ g ⁇ 0.95, 0.01 ⁇ h ⁇ 0.50, 0.01 ⁇ m ⁇ 0.30.
  • the M is selected from a combination of one or more of Ti, Mg, and Ca
  • the A is selected from a combination of two or three of B, P, and C
  • the molar ratio of B, P, and C is 2-4:0.1-1.5:0.1-1.5.
  • the positive electrode active material has a layered single crystal structure with an average particle size of 1-30 microns.
  • the tap density of the positive electrode active material is 1.33-2.5 g/cm 3 , and the pH value is below 12.6.
  • the present inventors have found through research that adding M element and A element to the positive electrode active material of the sodium ion battery, and simultaneously matching the ratio of sodium, nickel, iron, manganese and M, A, O elements, can realize the positive electrode active material of the sodium ion battery to form a perfect layered single crystal structure. Under the premise of exerting a higher gram specific capacity, the cycle performance at high temperature is obviously improved.
  • the present invention also provides a preparation method of the positive electrode active material of the above-mentioned sodium ion battery, the preparation method comprising the following steps:
  • the chemical formula of the nickel manganese hydroxide in step 1) is Ni a Mn b (OH) 2 , wherein, 0.05 ⁇ a ⁇ 0.95, 0.05 ⁇ b ⁇ 0.95, 1-ab>0.
  • the nickel salt in step 1) is selected from the combination of one or more of nickel sulfate, nickel chloride and nickel nitrate
  • the manganese salt is selected from the combination of one or more of manganese sulfate, manganese chloride and manganese nitrate
  • the hydroxide is selected from one or more of sodium hydroxide and potassium hydroxide
  • the complexing agent is selected from the combination of one or more of ethylenediamine, ethylenediamine tetraacetic acid, tartaric acid, citric acid, oxalic acid and ammonia.
  • step 1) the nickel salt and the manganese salt are formulated into an aqueous metal salt solution, and then mixed with an aqueous hydroxide solution and a complexing agent to obtain a mixed solution, and then the mixed solution is reacted at a pH of 9-12, 40-70° C. and stirred to form nickel-manganese hydroxide.
  • the total concentration of nickel ions and manganese ions in the metal salt solution is 0.5-2 mol/L, and the concentration of complexing agent in the mixed solution is 0.3-5 mol/L.
  • the stirring speed is 500-1200r/min, and aging, washing and drying are performed after the reaction to obtain Ni a Mn b (OH) 2 .
  • the iron source in step 2) is selected from one or more combinations of ferrous oxide, ferric oxide, and ferric oxide;
  • the sodium source is selected from one or both of sodium carbonate and sodium hydroxide.
  • the compound containing the M element described in step 2) is selected from titanium dioxide, aluminum oxide, magnesia, calcium oxide, calcium carbonate, zirconia, yttrium oxide, zinc oxide, niobium oxide, and tungsten oxide;
  • the compound containing the A element is selected from boric acid, boric oxide, sodium tetraborate, phosphorus pentoxide, phosphoric acid, sodium phosphate, sodium hypophosphite, glucose, sucrose, polyethylene glycol and polyvinyl alcohol.
  • step 2) according to the molar weight, the ratio of the total molar weight of the nickel and manganese in the nickel-manganese hydroxide, the iron in the iron source, the M element in the compound containing the M element, and the A element in the compound containing the A element to the molar weight of the sodium in the sodium source is 1:0.90-1.20.
  • the sanding time is 0.5-8 hours
  • the grinding body is a zirconia ball with a particle size of 0.1-0.8 mm
  • the sanding speed is 800-3000 rpm.
  • the solid content of the mixed slurry is 10%-60%, and the median diameter of the particles in the mixed slurry is 20-800nm.
  • the drying is spray drying
  • the rotational speed of the atomizing disk in the spray drying equipment is 1000-3000 rpm
  • the inlet air temperature is 150-300°C
  • the outlet air temperature is 80-120°C.
  • step 3 the sintering is carried out in air, the temperature of the sintering is 750-1000° C., and the sintering time is 5-25 hours.
  • pulverization is performed after sintering.
  • Ni and Mn elements that are easy to form uniform precipitation using their hydroxides as raw materials can improve the reaction activity; for Fe and M elements that are not easy to form uniform precipitation, using their oxides or compounds containing M elements as raw materials to ensure the stability of the corresponding element content.
  • Sanding after mixing nickel-manganese hydroxide, compounds containing M elements, compounds containing A elements, and sodium sources can ensure that various elements are fully mixed and evenly mixed, and spray drying can ensure that various raw materials do not have component segregation during the molding process.
  • the present invention also provides the use of the above-mentioned positive electrode active material of the sodium ion battery applied to the positive electrode of the sodium ion battery.
  • the present invention also provides a positive electrode material for a sodium ion battery, including a positive electrode active material, a binder and a conductive agent, and the positive electrode active material includes the aforementioned positive electrode active material for a sodium ion battery.
  • the present invention also provides a positive electrode of a sodium ion battery prepared from the aforementioned positive electrode material of a sodium ion battery.
  • the present invention also provides a sodium ion battery, which includes a positive electrode, and the positive electrode includes the aforementioned positive electrode of the sodium ion battery.
  • the present invention has the following technical advantages:
  • the positive electrode active material of the sodium ion battery of the present invention can form a perfect layered single crystal structure, the single crystal particle is large, the growth is dense, the tap density of the positive electrode active material is significantly improved, and the material has a low pH value, has stable surface properties, and has few side reactions with the electrolyte.
  • it can obviously improve the cycle performance at high temperature under the premise of ensuring a relatively high gram specific capacity.
  • the preparation method of the invention can stably prepare the positive active material of the sodium ion battery with excellent performance in large quantities.
  • Fig. 1 is the scanning electron micrograph of NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 B 0.05 O 2 that embodiment 1 makes;
  • Fig. 2 is the XRD pattern of NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 B 0.05 O 2 prepared in Example 1;
  • Fig. 3 is the charge-discharge curve diagram of NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 B 0.05 O 2 prepared in Example 1;
  • Figure 4 is a cycle diagram of NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 B 0.05 O 2 prepared in Example 1 at 2.0-4.0V/1C high temperature (60°C);
  • Fig. 5 is the scanning electron micrograph of NaNi 0.25 Fe 0.40 Mn 0.25 Ti 0.03 B 0.05 P 0.02 O 2 prepared in Example 2;
  • Fig. 6 is the XRD pattern of NaNi 0.25 Fe 0.40 Mn 0.25 Ti 0.03 B 0.05 P 0.02 O 2 prepared in Example 2;
  • Fig. 7 is the charge-discharge curve diagram of NaNi 0.25 Fe 0.40 Mn 0.25 Ti 0.03 B 0.05 P 0.02 O 2 prepared in Example 2;
  • Fig. 8 is a cycle diagram of NaNi 0.25 Fe 0.40 Mn 0.25 Ti 0.03 B 0.05 P 0.02 O 2 prepared in Example 2 at 2.0-4.0V/1C high temperature (60°C);
  • Fig. 9 is the scanning electron micrograph of NaNi 0.25 Fe 0.45 Mn 0.25 Ti 0.05 O 2 prepared in Comparative Example 1;
  • Figure 10 is the XRD pattern of NaNi 0.25 Fe 0.45 Mn 0.25 Ti 0.05 O 2 prepared in Comparative Example 1;
  • Fig. 11 is the charge-discharge curve diagram of NaNi 0.25 Fe 0.45 Mn 0.25 Ti 0.05 O 2 prepared in Comparative Example 1;
  • Fig. 12 is a cycle diagram of NaNi 0.25 Fe 0.45 Mn 0.25 Ti 0.05 O 2 prepared in Comparative Example 1 at 2.0-4.0V/1C high temperature (60°C).
  • a sodium-ion battery take 20 g of the prepared positive electrode active material, add 0.64 g of conductive agent SP and 0.64 g of PVDF dissolved in NMP, mix evenly, and coat it with aluminum foil to make an electrode sheet.
  • a button battery was assembled with a metal sodium sheet as the negative electrode, Celgard2700 as the separator, and 1mol/L NaPF 6 +EC:DEC(1:1)+5%FEC as the electrolyte.
  • This embodiment provides a positive electrode active material for a sodium ion battery, whose chemical formula is NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 B 0.05 O 2 , and the preparation method includes the following steps:
  • step (3) Add the metal salt solution obtained in step (1) and the sodium hydroxide solution and ammonia solution obtained in step (2) to the reaction kettle at a rate of 2.5L/h, 1.5L/h, and 0.2L/h respectively, control the reaction temperature to 50°C, the reaction pH to 11.5, the stirring speed to 650rpm, and react for 12 hours to prepare the precursor;
  • step (6) Put the slurry obtained in step (5) into a sand mill, grind for 3 hours, the grinding body is a zirconia ball with a particle size of 0.2 mm, and the grinding speed is 2500 rpm, and the mixed slurry with an average particle size of about 350 nm is obtained by grinding;
  • step (7) Move the mixed slurry prepared in step (6) into a mixing tank, fully stir, add pure water to adjust to a slurry with a solid content of 30 ⁇ 1%, spray and dry at the spray drying equipment with an atomization frequency of 35 Hz, an air inlet temperature of 190 °C, and an air outlet temperature of 85 °C.
  • the dried product is sintered at 850 to 940 °C for 12 hours in an air atmosphere furnace, cooled to below 80 °C, crushed, rolled, and pulverized to obtain the positive electrode active material of the sodium ion battery.
  • the sample name is NFM242-TB.
  • the scanning electron microscope image of NFM242-TB is shown in Figure 1, and it can be seen that the material has a single crystal morphology.
  • the XRD of NFM242-TB is shown in Figure 2. It can be seen that the material has a pure phase layered structure of ⁇ -NaFeO 2 type.
  • the charge-discharge curve of NFM242-TB is shown in Figure 3. It can be seen that within the voltage window of 2.0-4.0V, the discharge specific capacity at 0.1C rate is 124.8mAh/g.
  • the high-temperature cycle diagram of NFM242-TB is shown in Figure 4. It can be seen that at 60°C, within the voltage window of 2.0-4.0V, and at a rate of 1C, the capacity retention rate after 100 cycles is 89.04%.
  • the chemical formula of the positive electrode active material of the sodium ion battery in this embodiment is NaNi 0.25 Fe 0.40 Mn 0.25 Ti 0.03 B 0.05 P 0.02 O 2 .
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.8 mol of Fe 2 O 3 , 0.12 mol of TiO 2 , 0.2 mol of H 3 BO 3 , 0.08 mol of H 3 PO 4 , and 2.0 mol of Na 2 CO 3 .
  • the sample name is NFM242-TBP.
  • NFM242-TBP The scanning electron microscope image of NFM242-TBP is shown in Figure 5, and it can be seen that the material has a single crystal morphology.
  • the XRD of NFM242-TBP is shown in Figure 6. It can be seen that the material has a pure phase layered structure of ⁇ -NaFeO 2 type.
  • the charge-discharge curve of NFM242-TBP is shown in Figure 7. It can be seen that within the voltage window of 2.0-4.0V, the discharge specific capacity at 0.1C rate is 125mAh/g.
  • the high-temperature cycle diagram of NFM242-TBP is shown in Figure 8. It can be seen that at 60°C, within the voltage window of 2.0-4.0V, and at a rate of 1C, the capacity retention rate after 100 cycles is 93.31%.
  • the chemical formula of the positive electrode active material of the sodium ion battery in this embodiment is NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 P 0.05 O 2 .
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.8 mol of Fe 2 O 3 , 0.20 mol of TiO 2 , 0.2 mol of H 3 PO 4 , and 2.0 mol of Na 2 CO 3 , and adding all raw materials into 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the final NaNi 0.25 Fe 0.4 Mn 0.25 Ti 0.05 P 0.05 O 2 positive electrode active material for sodium ion batteries is obtained, and the sample name is NFM242-TP.
  • the chemical formula of the positive electrode active material of the sodium ion battery in this embodiment is NaNi 0.25 Fe 0.4 Mn 0.25 Ca 0.05 B 0.05 O 2 .
  • the preparation method is basically the same as in Example 1, except that in step (5), 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.8 mol of Fe 2 O 3 , 0.2 mol of CaCO 3 , 0.2 mol of H 3 BO 3 , and 2.0 mol of Na 2 CO 3 are taken, and all raw materials are added to 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the final NaNi 0.25 Fe 0.4 Mn 0.25 Ca 0.05 B 0.05 O 2 positive electrode active material for sodium ion batteries is obtained, and the sample name is NFM242-CaB.
  • the chemical formula of the positive electrode active material of the sodium ion battery in this embodiment is NaNi 0.25 Fe 0.4 Mn 0.25 Ca 0.05 P 0.05 O 2 .
  • the preparation method is basically the same as in Example 1, except that in step (5), 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.8 mol of Fe 2 O 3 , 0.2 mol of CaCO 3 , 0.2 mol of H 3 PO 4 , and 2.0 mol of Na 2 CO 3 are taken, and all raw materials are added to 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the final NaNi 0.25 Fe 0.4 Mn 0.25 Ca 0.05 P 0.05 O 2 positive electrode active material for sodium ion batteries is obtained, and the sample name is NFM242-CaP.
  • the chemical formula of the positive electrode active material of the sodium ion battery in this embodiment is NaNi 0.25 Fe 0.40 Mn 0.25 Ca 0.03 B 0.05 P 0.02 O 2 .
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.8 mol of Fe 2 O 3 , 0.12 mol of CaCO 3 , 0.2 mol of H 3 BO 3 , 0.08 mol of H 3 PO 4 , and 2.0 mol of Na 2 CO 3 , adding all raw materials into 3.5 L of water to adjust Make slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the final NaNi 0.25 Fe 0.40 Mn 0.25 Ca 0.03 B 0.05 P 0.02 O 2 positive electrode active material for sodium ion batteries is obtained, and the sample name is NFM242-CaBP.
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.9 mol of Fe 2 O 3 , 0.2 mol of TiO 2 , and 2.0 mol of Na 2 CO 3 , and adding all the raw materials into 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the final NaNi 0.25 Fe 0.45 Mn 0.25 Ti 0.05 O 2 positive electrode active material for sodium ion batteries is obtained, and the sample name is NFM242-T.
  • NFM242-T The scanning electron microscope image of NFM242-T is shown in Figure 9. It can be seen that the material is agglomerated into a loose spherical structure of fine primary particles, and cannot form a single crystal structure.
  • the XRD of NFM242-T is shown in Figure 10. It can be seen that the material has a pure phase layered structure of ⁇ -NaFeO 2 type.
  • the charge-discharge curve of NFM242-T is shown in Figure 11. It can be seen that within the voltage window of 2.0-4.0V, the discharge specific capacity at 0.1C rate is 126.6mAh/g.
  • the high-temperature cycle diagram of NFM242-T is shown in Figure 12. It can be seen that at 60°C, within the voltage window of 2.0-4.0V, and at a rate of 1C, the capacity retention rate after 100 cycles is 82.8%.
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 0.9 mol of Fe 2 O 3 , 0.2 mol of CaCO 3 , and 2.0 mol of Na 2 CO 3 , and adding all the raw materials into 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the NaNi 0.25 Fe 0.45 Mn 0.25 Ca 0.05 O 2 positive electrode active material of the sodium ion battery was finally obtained, and the sample name was NFM242-Ca.
  • step (5) is replaced by taking 2.0 mol of Ni 0.5 Mn 0.5 (OH) 2 , 1.0 mol of Fe 2 O 3 , and 2.0 mol of Na 2 CO 3 , and adding all the raw materials into 3.5 L of water to prepare a slurry. After sand milling, spray drying, sintering, jaw crushing, rolling, and crushing, the NaNi 0.25 Fe 0.50 Mn 0.25 O 2 positive electrode active material of the sodium ion battery was finally obtained, and the sample name was NFM252.
  • the positive electrode active material prepared in the above-mentioned Examples 1-7 and Comparative Example 1-2 was used for the performance test of the sodium ion battery.
  • the manufacturing method of the sodium ion battery was as follows: 20 g of the prepared positive electrode active material was weighed, 0.64 g of the conductive agent SP and 0.64 g of PVDF dissolved in NMP were added, mixed evenly, and coated on the aluminum foil to form an electrode sheet.
  • a button battery was assembled with a metal sodium sheet as the negative electrode, Celgard2700 as the separator, and 1mol/L NaPF 6 +EC:DEC(1:1)+5%FEC as the electrolyte.
  • the test voltage range is 2.0-4.0V, and the 0.1C current is 13mA.
  • the test results are shown in Table 2 below.
  • the present invention can realize the formation of a perfect layered single crystal structure of the positive electrode active material, and the single crystal particles are large and densely grown, the tap density of the positive electrode active material is significantly increased, and the pH value is reduced.

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Abstract

本发明公开了一种钠离子电池正极活性物质及其制备方法、应用。该钠离子电池正极活性物质的化学式为Na xNi yFe zMn gM hA mO 2，其中，M为选自Ti、Al、Mg、Ca、Zr、Y、Zn、Nb、W中的一种或多种的组合，A为选自B、P、C中的一种或多种的组合，0.80≤x≤1.40，0.05≤y≤0.95，0.05≤z≤0.95，0.05≤g≤0.95，0.01≤h≤0.50，0.01≤m≤0.30。本发明通过在三元铁锰镍钠离子电池正极活性物质中添加M元素和A元素，同时配合各元素配比，可以实现钠离子电池正极活性物质形成完美的层状单晶结构，且颗粒大，最终实现活性物质稳定，应用于钠离子电池时在保证发挥较高克比容量的前提下，高温下循环性能明显提高。

Description

一种钠离子电池正极活性物质及其制备方法、应用 技术领域
本发明属于钠离子电池领域，具体涉及一种钠离子电池正极活性物质及其制备方法、应用。
背景技术
锂离子电池已在电动汽车、中大型储能电站、电动两轮车、电动工具、便携式电子设备等领域得到广泛应用。但随着锂离子电池在电动汽车和中大型储能电站方面的爆发式增长，锂资源结构性短缺的问题凸显，导致锂盐价格暴涨，锂离子电池成本激增。钠离子电池与锂离子电池具有相似的电化学性质，且钠离子电池资源丰富，成本较低，近年来成为热门发展方向，有望在电动两轮车和中大型储能电站领域得到广泛应用。
钠离子电池由于钠离子的半径大，可供选择的正极活性物质比较有限，目前，已展现出潜在应用前景的钠离子电池正极活性物质包括普鲁士蓝、层状氧化物、聚阴离子三类体系。其中O3结构层状氧化物体系，类似锂离子电池中三元正极活性物质，具有容量高、压实密度高等优点，被视为最具潜力的正极材料，被国内外钠离子电池公司采用。
中国专利CN109817970A公开了一种单晶钠离子电池电极材料的制备方法，将铁盐、锰盐和M盐的混合水溶液、沉淀剂、络合剂和分散剂混合反应后，获得的固体即为电池电极材料前驱体；将前驱体和钠盐混合，烧结，冷却，即得单晶钠离子电池电极材料；其中分散剂为聚丙烯酸铵。当不采用上述特定的聚丙烯酸铵分散剂时，晶粒的晶体形貌不明显，无法形成微米级大颗粒单晶，相应电池电极材料的放电容量和容量保持率也较低。
层状氧化物正极活性物质展现了优异的电化学性能，但其存在充放电过程中结构相变多、空气存储性能差、表面碱性高、与电解液副反应等问题，极大制约了该类活性物质的规模商业化应用。
发明内容
本发明的目的是针对现有技术的缺点和不足，提供一种钠离子电池正极活性物质，该活性物质可以保证钠离子电池优异的克容量性能，提高高温下的循环性能，同时能够形成稳定的单晶结构，表面碱性低。
为解决以上技术问题，本发明采取的一种技术方案如下：
一种钠离子电池正极活性物质，所述正极活性物质的化学式为Na xNi yFe zMn gM hA mO 2，其中，M为选自Ti、Al、Mg、Ca、Zr、Y、Zn、Nb、W中的一种或多种的组合，A为选自B、P、C中的一种或多种的组合，0.80≤x≤1.40，0.05≤y≤0.95，0.05≤z≤0.95，0.05≤g≤0.95，0.01≤h≤0.50，0.01≤m≤0.30。
根据本发明的一些优选且具体的方面，所述化学式Na xNi yFe zMn gM hA mO 2中，0.90≤x≤1.20，1.2-(y+z+g+h)≥0。
根据本发明的一些优选且具体的方面，所述化学式Na xNi yFe zMn gM hA mO 2中，0.95≤x≤1.05，0.1≤y≤0.5，0.1≤z≤0.6，0.1≤g≤0.5，0.01≤h≤0.3，0.01≤m≤0.2。
根据本发明的一些优选且具体的方面，所述化学式Na xNi yFe zMn gM hA mO 2中，0.98≤x≤1.03，0.1≤y≤0.4，0.2≤z≤0.5，0.1≤g≤0.4，0.01≤h≤0.2，0.01≤m≤0.1。
在本发明的一些具体实施方案中，所述M选自Ti、Mg、Ca中的一种或多种的组合，所述A选自B、P、C中两种或三种的组合，所述B、P、C的摩尔比为2-4:0.1-1.5:0.1-1.5。
在本发明的一些具体实施方案中，所述正极活性物质为层状单晶结构，平均粒径为1-30微米。
在本发明的一些具体实施方案中，所述正极活性物质的振实密度为1.33-2.5g/cm 3，pH值为12.6以下。
本发明人通过研究发现，在钠离子电池正极活性物质中，添加M元素和A元素，同时配合钠、镍、铁、锰元素和M、A、O元素的配比，可以实现钠离子电池正极活性物质形成完美的层状单晶结构，该活性物质能够形成大颗粒，且颗粒生长密实，活性物质的振实密度明显提高，且该物质的pH值较低，表面碱性低，具有稳定的表面性质，与电解液副反应少，同时用于钠离子电池时，能够在保证发挥较高的克比容量的前提下，明显提高高温下的循环性能。
本发明的钠离子电池正极活性物质中，各种元素起到不同的作用，其中Ni，Mn元素使得钠离子电池具有较高的克容量发挥；Fe元素具有克容量发挥和提高材料放电电压的双重功效；M元素提高活性物质的稳定性；B元素促使活性物质形成大颗粒单晶结构，提高材料的压实密度；P元素能提高活性物质高温下的循环性能；此外，各种元素还存在协同相互作用，共同发挥作用，使得本发明的钠离子电池正极活性物质实现上述各项优异性能，明显提高了高温下的循环性能。
本发明还提供了上述钠离子电池正极活性物质的制备方法，所述制备方法包括如下步骤：
1)使镍盐、锰盐与氢氧化物在络合剂的存在下反应生成镍锰氢氧化物；
2)将镍锰氢氧化物、铁源、含有M元素的化合物、含有A元素的化合物和钠源
加水制成浆料，砂磨后得到混合浆料；
3)将所述混合浆料干燥、烧结，得到所述钠离子电池正极活性物质。
进一步地，步骤1)中所述镍锰氢氧化物的化学式为Ni aMn b(OH) 2，其中，0.05≤a≤0.95，0.05≤b≤0.95，1-a-b>0。
进一步地，步骤1)中所述镍盐选自硫酸镍、氯化镍和硝酸镍中的一种或多种的组合，所述锰盐选自硫酸锰、氯化锰和硝酸锰中的一种或多种的组合，所述氢氧化物选自氢氧化钠和氢氧化钾中的一种或两种，所述络合剂选自乙二胺、乙二胺四乙酸、酒石酸、柠檬酸、草酸和氨水中的一种或几种的组合。
在本发明的一些实施方案中，步骤1)中将镍盐、锰盐配成金属盐水溶液，再与氢氧化物的水溶液、络合剂混合得到混合溶液，然后使混合溶液在pH为9-12、40-70℃以及搅拌下反应生成镍锰氢氧化物。
更优选地，所述金属盐水溶液中镍离子、锰离子的总浓度为0.5-2mol/L，所述混合溶液中络合剂的浓度为0.3-5mol/L。
更优选地，所述搅拌的速度为500-1200r/min，反应后陈化、洗涤、烘干得到Ni aMn b(OH) 2。
在本发明的一些实施方案中，步骤2)中所述铁源选自氧化亚铁、三氧化二铁、四氧化三铁中的一种或多种的组合；所述钠源选自碳酸钠和氢氧化钠中的一种或两种。
在本发明的一些实施方案中，步骤2)中所述含有M元素的化合物选自二氧化钛、三氧化二铝、氧化镁、氧化钙、碳酸钙、氧化锆、氧化钇、氧化锌、氧化铌、氧化钨；所述含有A元素的化合物选自硼酸、氧化硼、四硼酸钠、五氧化二磷、磷酸、磷酸钠、亚次磷酸钠、葡萄糖、蔗糖、聚乙二醇和聚乙烯醇中的一种或多种的组合。
在本发明的一些实施方案中，步骤2)中，按照摩尔量，所述镍锰氢氧化物中的镍、锰，铁源中的铁，含有M元素的化合物中的M元素以及含有A元素的化合物中的A元素的合计摩尔量，与所述钠源中的钠的摩尔量之比为1：0.90～1.20。
在本发明的一些实施方案中，步骤2)中，所述砂磨的时间为0.5～8h，研磨体为粒径0.1～0.8mm的氧化锆球，砂磨速度为800～3000rpm。
在本发明的一些实施方案中，所述混合浆料的固含量为10％～60％，所述混合浆料中颗粒的中值粒径为20～800nm。
在本发明的一些实施方案中，步骤3)中，所述干燥为喷雾干燥，喷雾干燥设备中雾化盘转速为1000～3000rpm，进风温度为150～300℃，出风温度为80～120℃。
在本发明的一些实施方案中，步骤3)中，所述烧结在空气中进行，所述烧结的温度为750～1000℃，时间为5～25h。优选地，烧结后进行粉碎。
在本发明的制备方法中，对于容易形成均匀沉淀的Ni、Mn元素，采用其氢氧化物作为原料能提高反应活性，对于不容易形成均匀沉淀的Fe、M元素，采用其氧化物或含有M元素的化合物作为原材料，保证相应元素含量的稳定性。将镍锰氢氧化物、含有M元素的化合物、含有A元素的化合物，钠源混合后砂磨，可以保证各种元素充分地混合均匀，采用喷雾干燥可保证多种原材料在成型的过程中不出现组分偏析。
本发明还提供了上述钠离子电池正极活性物质应用于钠离子电池正极的用途。
本发明还提供了一种钠离子电池正极材料，包括正极活性物质、粘结剂和导电剂，所述正极活性物质包括前述钠离子电池正极活性物质。
本发明还提供了一种由前述钠离子电池正极材料制备得到的钠离子电池正极。
本发明还提供了一种钠离子电池，包括正极，所述正极包括前述钠离子电池正极。
与现有技术相比，本发明具有如下技术优势：
本发明的钠离子电池正极活性物质可以形成完美的层状单晶结构，其单晶颗粒大，生长密实，正极活性物质的振实密度明显提高，且该物质pH值较低，具有稳定的表面性质，与电解液副反应少，同时用于钠离子电池时，能够在保证发挥较高的克比容量的前提下，明显提高高温下的循环性能。
本发明的制备方法能够大批量、稳定的制备出性能优异的钠离子电池正极活性物质。
附图说明
图1为实施例1制得的NaNi 0.25Fe 0.4Mn 0.25Ti 0.05B 0.05O 2的扫描电镜图；
图2为实施例1制得的NaNi 0.25Fe 0.4Mn 0.25Ti 0.05B 0.05O 2的XRD图；
图3为实施例1制得的NaNi 0.25Fe 0.4Mn 0.25Ti 0.05B 0.05O 2的充放电曲线图；
图4为实施例1制得的NaNi 0.25Fe 0.4Mn 0.25Ti 0.05B 0.05O 2在2.0～4.0V/1C高温(60℃)循环图；
图5为实施例2制得的NaNi 0.25Fe 0.40Mn 0.25Ti 0.03B 0.05P 0.02O 2的扫描电镜图；
图6为实施例2制得的NaNi 0.25Fe 0.40Mn 0.25Ti 0.03B 0.05P 0.02O 2的XRD图；
图7为实施例2制得的NaNi 0.25Fe 0.40Mn 0.25Ti 0.03B 0.05P 0.02O 2的充放电曲线图；
图8为实施例2制得的NaNi 0.25Fe 0.40Mn 0.25Ti 0.03B 0.05P 0.02O 2在2.0～4.0V/1C高温(60℃)循环图；
图9为对比例1制得的NaNi 0.25Fe 0.45Mn 0.25Ti 0.05O 2的扫描电镜图；
图10为对比例1制得的NaNi 0.25Fe 0.45Mn 0.25Ti 0.05O 2的XRD图；
图11为对比例1制得的NaNi 0.25Fe 0.45Mn 0.25Ti 0.05O 2的充放电曲线图；
图12为对比例1制得的NaNi 0.25Fe 0.45Mn 0.25Ti 0.05O 2在2.0～4.0V/1C高温(60℃)循环图。
具体实施方式
为了更好地理解本发明的内容，下面结合具体实施例和附图作进一步说明。应理解，这些实施例仅用于对发明的进一步说明，而不用于限制本发明的范围。此外应理解，在阅读了本发明的内容后，在不脱离本发明原理的前提下，该领域的技术人员对本发明做出的若干改进和调整，仍属于本发明的保护范围。下述中，如无特殊说明，所有的原料均来自于商购获得。
以下各实施例和对比例中，采用如下方法进行充放电曲线和高温循环性能测试：首先制备钠离子电池：称取20g准备好的正极活性物质，加入0.64g导电剂SP和0.64g溶于NMP的PVDF，混合均匀后涂覆与铝箔上制成电极片。在氩气气氛的手套箱中，以金属钠片为负极，Celgard2700为隔膜，1mol/L NaPF 6+EC:DEC(1:1)+5％FEC为电解液，组装成纽扣电池。然后在电压范围为2.0-4.0V，充放电倍率为0.1C，电流为13mA，测试温度为25±2℃下测试充放电曲线，在电压范围为2.0-4.0V，充放电倍率为1C，电流为130mA，60℃下测试循环100周的循环性能。
实施例1
本实施例提供一种钠离子电池正极活性物质，其化学式为NaNi 0.25Fe 0.4Mn 0.25Ti 0.05B 0.05O 2，制备方法包括以下步骤：
(1)将硫酸镍、硫酸锰按Ni:Mn摩尔比＝1:1加入纯水中，配制成金属元素的总浓度为1.3mol/L的溶液；
(2)配制4.0mol/L的氢氧化钠溶液和5.0mol/L的氨水溶液；
(3)将步骤(1)所得金属盐溶液和步骤(2)所得的氢氧化钠溶液、氨水溶液分别以2.5L/h、1.5L/h、0.2L/h的速度加入到反应釜中，控制反应温度为50℃，反应pH为11.5，搅拌速度为650rpm，反应12h制得前驱体；
(4)将上述前驱体经纯水洗涤，过滤，烘干后得到Ni 0.5Mn 0.5(OH) 2；
(5)取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.2mol的TiO 2，0.2mol的H 3BO 3，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料；
(6)将步骤(5)所得浆料加入砂磨机，研磨3h，研磨体为粒径0.2mm的氧化锆球，砂磨转速为2500rpm，研磨得到平均粒径约350nm的混合浆料；
(7)将步骤(6)制得的混合浆料移入搅拌桶中，充分搅拌，加纯水调成固含量为30±1％的浆料，在喷雾干燥设备的雾化频率为35Hz，进风温度为190℃，出风温度为85℃条件下喷雾干燥，干燥后产物在空气气氛炉中，于850～940℃下烧结12小时，冷却至80℃以下，鄂破、对辊、粉碎，得到钠离子电池正极活性物质，样品名称为NFM242-TB。
NFM242-TB的扫描电镜图如图1所示，可看出该材料为单晶形貌。NFM242-TB的XRD如图2所示，可以看出，该材料为α-NaFeO 2型纯相层状结构。NFM242-TB的充放电曲线图如图3所示，可以看出，在2.0～4.0V的电压窗口内，0.1C倍率下的放电比容量为124.8mAh/g。NFM242-TB的高温循环图如图4所示，可以看出，在60℃，2.0～4.0V的电压窗口内，1C倍率下，循环100次后容量保持率为89.04％。
实施例2
本实施例的钠离子电池正极活性物质的化学式为NaNi 0.25Fe 0.40Mn 0.25Ti 0.03B 0.05P 0.02O 2。
制备方法基本同实施例1，区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.12mol的TiO 2，0.2mol的H 3BO 3，0.08mol的H 3PO 4，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。样品名称为NFM242-TBP。
NFM242-TBP的扫描电镜图如图5所示，可看出该材料为单晶形貌。NFM242-TBP的XRD如图6所示，可以看出，可以看出，该材料为α-NaFeO 2型纯相层状结构。NFM242-TBP的充放电曲线图如图7所示，可以看出，在2.0～4.0V的电压窗口内，0.1C倍率下的放电比容量在125mAh/g。NFM242-TBP的高温循环图如图8所示，可以看出，在60℃，2.0～4.0V的电压窗口内，1C倍率下，循环100次后容量保持率为93.31％。
实施例3
本实施例的钠离子电池正极活性物质的化学式为NaNi 0.25Fe 0.4Mn 0.25Ti 0.05P 0.05O 2。
制备方法基本同实施例1，区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.20mol的TiO 2，0.2mol的H 3PO 4，2.0mol的Na 2CO 3， 将所有原材料加入到3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.4Mn 0.25Ti 0.05P 0.05O 2，样品名称为NFM242-TP。
实施例4
本实施例的钠离子电池正极活性物质的化学式为NaNi 0.25Fe 0.4Mn 0.25Ca 0.05B 0.05O 2。
制备方法基本同实施例1，区别仅在于：步骤(5)取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.2mol的CaCO 3，0.2mol的H 3BO 3，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.4Mn 0.25Ca 0.05B 0.05O 2，样品名称为NFM242-CaB。
实施例5
本实施例的钠离子电池正极活性物质的化学式为NaNi 0.25Fe 0.4Mn 0.25Ca 0.05P 0.05O 2。
制备方法基本同实施例1，区别仅在于：步骤(5)取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.2mol的CaCO 3，0.2mol的H 3PO 4，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.4Mn 0.25Ca 0.05P 0.05O 2，样品名称为NFM242-CaP。
实施例6
本实施例的钠离子电池正极活性物质的化学式为NaNi 0.25Fe 0.40Mn 0.25Ca 0.03B 0.05P 0.02O 2。
制备方法基本同实施例1，区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.8mol的Fe 2O 3，0.12mol的CaCO 3，0.2mol的H 3BO 3，0.08mol的H 3PO 4，2.0mol的Na 2CO 3，将所有原材料加入3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.40Mn 0.25Ca 0.03B 0.05P 0.02O 2，样品名称为NFM242-CaBP。
对比例1
基本同实施例1，其区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.9mol的Fe 2O 3，0.2mol的TiO 2，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。 经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.45Mn 0.25Ti 0.05O 2，样品名称为NFM242-T。
NFM242-T的扫描电镜图如图9所示，可看出该材料为细小的一次颗粒团聚成松散的球状结构，无法形成单晶结构。NFM242-T的XRD如图10所示，可以看出，该材料为α-NaFeO 2型纯相层状结构。NFM242-T的充放电曲线图如图11所示，可以看出，在2.0～4.0V的电压窗口内，0.1C倍率下的放电比容量为126.6mAh/g。NFM242-T的高温循环图如图12所示，可以看出，在60℃，2.0～4.0V的电压窗口内，1C倍率下，循环100次后容量保持率为82.8％。
对比例2
基本同实施例1，其区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，0.9mol的Fe 2O 3，0.2mol的CaCO 3，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.45Mn 0.25Ca 0.05O 2，样品名称为NFM242-Ca。
对比例3
基本同实施例1，其区别仅在于：步骤(5)替换为取2.0mol的Ni 0.5Mn 0.5(OH) 2，1.0mol的Fe 2O 3，2.0mol的Na 2CO 3，将所有原材料加入到3.5L水中调制成浆料。经砂磨、喷雾干燥、烧结、鄂破、对辊、粉碎，最终得到的钠离子电池正极活性物质的NaNi 0.25Fe 0.50Mn 0.25O 2，样品名称为NFM252。
性能测试
将上述实施例1-7以及对比例1-3所制得的正极活性物质进行物化性能测试，其中pH值测试方法为：称取5g准备好的层状氧化物正极材料分散到50mL去离子水中，在磁力搅拌器上搅拌5min，然后在25℃下静置30min，再过滤混合液去滤液进行测试，用pH计测试滤液的pH值。物化性能结果如下表1所示。
表1、正极活性物质的物理性能
Figure PCTCN2022082410-appb-000001
将上述实施例1-7以及对比例1-2所制得的正极活性物质用于钠离子电池性能测试，钠离子电池制作方法为：称取20g准备好的正极活性物质，加入0.64g导电剂SP和0.64g溶于NMP的PVDF，混合均匀后涂覆与铝箔上制成电极片。在氩气气氛的手套箱中，以金属钠片为负极，Celgard2700为隔膜，1mol/L NaPF 6+EC:DEC(1:1)+5％FEC为电解液，组装成纽扣电池。测试电压区间为2.0～4.0V，0.1C电流为13mA，测试结果如下表2所示。
表2、钠离子电池的性能
Figure PCTCN2022082410-appb-000002
由上表1-2可知，本发明通过在钠离子电池正极活性物质中添加B、P元素，并控制所有元素的配比，可以实现正极活性物质形成完美的层状单晶结构，且单晶颗粒大，生长密实，正极活性物质的振实密度明显提高，pH值降低，将该正极活性物质用于钠离子电池时，能够在保证发挥较高的克比容量的前提下，明显提高高温下的循环性能。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (23)

  1. 一种钠离子电池正极活性物质，其特征在于：所述正极活性物质的化学式为Na xNi yFe zMn gM hA mO 2，其中，M为选自Ti、Al、Mg、Ca、Zr、Y、Zn、Nb、W中的一种或多种的组合，A为选自B、P、C中的一种或多种的组合，0.80≤x≤1.40，0.05≤y≤0.95，0.05≤z≤0.95，0.05≤g≤0.95，0.01≤h≤0.50，0.01≤m≤0.30。
  2. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述化学式Na xNi yFe zMn gM hA mO 2中，0.90≤x≤1.20，1.2-(y+z+g+h)≥0。
  3. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述化学式Na xNi yFe zMn gM hA mO 2中，0.95≤x≤1.05，0.1≤y≤0.5，0.1≤z≤0.6，0.1≤g≤0.5，0.01≤h≤0.3，0.01≤m≤0.2。
  4. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述化学式Na xNi yFe zMn gM hA mO 2中，0.98≤x≤1.03，0.1≤y≤0.4，0.2≤z≤0.5，0.1≤g≤0.4，0.01≤h≤0.2，0.01≤m≤0.1。
  5. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述M选自Ti、Mg、Ca中的一种或多种的组合，所述A选自B、P、C中两种或三种的组合，所述B、P、C的摩尔比为2-4:0.1-1.5:0.1-1.5。
  6. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述正极活性物质为层状单晶结构，平均粒径为1-30微米。
  7. 根据权利要求1所述的钠离子电池正极活性物质，其特征在于：所述正极活性物质的振实密度为1.33-2.5g/cm 3，pH值为12.6以下。
  8. 一种制备权利要求1-7任一项所述钠离子电池正极活性物质的方法，其特征在于：所述方法包括以下步骤：
    1)使镍盐、锰盐与氢氧化物在络合剂的存在下反应生成镍锰氢氧化物；
    2)将镍锰氢氧化物、铁源、含有M元素的化合物、含有A元素的化合物和钠源加水制成浆料，砂磨后得到混合浆料；
    3)将所述混合浆料干燥、烧结，得到所述钠离子电池正极活性物质。
  9. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤1)中所述镍锰氢氧化物的化学式为Ni aMn b(OH) 2，其中，0.05≤a≤0.95，0.05≤b≤0.95，1-a-b>0。
  10. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤1)中所述镍盐选自硫酸镍、氯化镍和硝酸镍中的一种或多种的组合，所述锰盐选自硫酸 锰、氯化锰和硝酸锰中的一种或多种的组合，所述氢氧化物选自氢氧化钠和氢氧化钾中的一种或两种，所述络合剂选自乙二胺、乙二胺四乙酸、酒石酸、柠檬酸、草酸和氨水中的一种或几种的组合。
  11. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤1)中将镍盐、锰盐配成金属盐水溶液，再与氢氧化物的水溶液、络合剂混合得到混合溶液，然后使混合溶液在pH为9-12、40-70℃以及搅拌下反应生成镍锰氢氧化物。
  12. 根据权利要求11所述的制备钠离子电池正极活性物质的方法，其特征在于：所述金属盐水溶液中镍离子、锰离子的总浓度为0.5-2mol/L，所述混合溶液中络合剂的浓度为0.3-5mol/L。
  13. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤2)中所述铁源选自氧化亚铁、三氧化二铁、四氧化三铁中的一种或多种的组合；所述钠源选自碳酸钠和氢氧化钠中的一种或两种。
  14. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤2)中所述含有M元素的化合物选自二氧化钛、三氧化二铝、氧化镁、氧化钙、碳酸钙、氧化锆、氧化钇、氧化锌、氧化铌、氧化钨；所述含有A元素的化合物选自硼酸、氧化硼、四硼酸钠、五氧化二磷、磷酸、磷酸钠、亚次磷酸钠、葡萄糖、蔗糖、聚乙二醇和聚乙烯醇中的一种或多种的组合。
  15. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤2)中，按照摩尔量，所述镍锰氢氧化物中的镍、锰，铁源中的铁，含有M元素的化合物中的M元素以及含有A元素的化合物中的A元素的合计摩尔量，与所述钠源中的钠的摩尔量之比为1：0.90～1.20。
  16. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤2)中，所述砂磨的时间为0.5～8h，研磨体为粒径0.1～0.8mm的氧化锆球，砂磨速度为800～3000rpm。
  17. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：所述混合浆料中颗粒的中值粒径为20～800nm，所述混合浆料的固含量为10％～60％。
  18. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤3)中，所述干燥为喷雾干燥，喷雾干燥设备中雾化盘转速为1000～3000rpm，进风温度为150～300℃，出风温度为80～120℃。
  19. 根据权利要求8所述的制备钠离子电池正极活性物质的方法，其特征在于：步骤 3)中，所述烧结在空气中进行，所述烧结的温度为750～1000℃，时间为5～25h。
  20. 一种权利要求1-7任一项所述钠离子电池正极活性物质应用于钠离子电池正极的用途。
  21. 一种钠离子电池正极材料，包括正极活性物质、粘结剂和导电剂，其特征在于：所述正极活性物质包括权利要求1-7任一项所述的钠离子电池正极活性物质。
  22. 一种钠离子电池正极，其特征在于：所述钠离子电池正极由权利要求21所述的钠离子电池正极材料制备得到。
  23. 一种钠离子电池，包括正极，其特征在于：所述正极包括权利要求22所述的钠离子电池正极。
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EP3415470A1 (en) * 2017-06-14 2018-12-19 Karlsruher Institut für Technologie Boron-doped sodium-ion cathode material, method of producing same and its use
CN109817970A (zh) 2019-01-31 2019-05-28 上海紫剑化工科技有限公司 一种单晶钠离子电池电极材料及其制备方法
CN113471431A (zh) * 2020-09-17 2021-10-01 中南大学 一种NaMn0.5Ni0.5BxO2材料及其制备和在钠离子电池中的应用
CN112310390A (zh) * 2020-10-29 2021-02-02 福建师范大学 O3型钠离子电池层状正极材料以及通过元素掺杂提升材料纯度的方法

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CN117012949A (zh) * 2023-10-07 2023-11-07 有研(广东)新材料技术研究院 低镍高能量密度层状钠离子电池正极材料及其制备方法
CN117012949B (zh) * 2023-10-07 2024-01-26 有研(广东)新材料技术研究院 低镍层状钠离子电池正极材料及其制备方法

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