WO2024259816A1 - 正极活性材料及其制备方法、正极极片、电池和用电设备 - Google Patents

正极活性材料及其制备方法、正极极片、电池和用电设备 Download PDF

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WO2024259816A1
WO2024259816A1 PCT/CN2023/119789 CN2023119789W WO2024259816A1 WO 2024259816 A1 WO2024259816 A1 WO 2024259816A1 CN 2023119789 W CN2023119789 W CN 2023119789W WO 2024259816 A1 WO2024259816 A1 WO 2024259816A1
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Prior art keywords
positive electrode
active material
electrode active
source
battery
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English (en)
French (fr)
Inventor
吴凯
栾柯
梁子彬
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP23942083.9A priority Critical patent/EP4730420A1/en
Priority to JP2025553884A priority patent/JP2026508647A/ja
Priority to KR1020257030237A priority patent/KR20250141257A/ko
Publication of WO2024259816A1 publication Critical patent/WO2024259816A1/zh
Priority to US19/324,392 priority patent/US20260024760A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/70—Complex oxides containing nickel and at least one other metal element containing rare earths, e.g. LaNiO3 
    • C—CHEMISTRY; METALLURGY
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/66—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
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    • 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
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    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
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    • 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
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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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    • C01P2006/10—Solid density
    • 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
    • C01P2006/00—Physical properties of 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
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    • C01P2006/40—Electric properties
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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 present application relates to the technical field of secondary batteries, and in particular to a positive electrode active material and a preparation method thereof, a positive electrode sheet, a battery and an electrical device.
  • Secondary batteries are not only used in energy storage power systems such as hydropower, thermal, wind and solar power stations, but are also widely used in electric transportation vehicles such as electric bicycles, electric motorcycles, electric cars, as well as in military equipment, aerospace and other fields.
  • Sodium ion battery is a kind of secondary battery, and layered transition metal oxide is a commonly used positive electrode active material for sodium ion battery. However, the capacity retention rate of existing sodium ion batteries containing layered transition metal oxide is low.
  • the present application provides a positive electrode active material, aiming to solve the problem of low capacity retention rate of batteries containing the positive electrode active material.
  • the first aspect of the present application provides a positive electrode active material, wherein the positive electrode active material comprises: Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f ,
  • M1 includes rare earth elements
  • the main material of the positive electrode active material of the present application includes NiFeMn, and is doped with rare earth element M1 and doping element M2, and the above content of Fe can improve the specific capacity of the material.
  • the rare earth element M1 has a large radius and will form a dense and uniform doping layer on the surface of the positive electrode active material.
  • the doping layer can effectively block the intrusion of water vapor from the surface of the positive electrode active material to the bulk phase, thereby improving the structural stability of the material.
  • the doping layer can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the material, thereby improving the structural stability of the material and improving the capacity retention rate of the battery containing it.
  • the doping element M2 is distributed in the bulk phase of the positive electrode active material, and can form a strong chemical bond with O in the positive electrode active material, inhibit the release of Na ions in the positive electrode active material from the bulk phase, and can reduce the change in the interlayer spacing of the positive electrode active material, delay the occurrence of phase change, and improve the cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery.
  • the ratio d/c of the rare earth element M1 to Mn in the positive electrode active material is within the above range, which is beneficial to improving the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing the same.
  • the rare earth elements include La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, At least one of Tm, Yb and Lu.
  • M1 uses at least one of the above rare earth elements to form a dense and uniform doping layer on the surface of the positive electrode active material, reducing the probability of phase change of the positive electrode active material, improving the cycle performance of the positive electrode active material, and thus improving the capacity retention rate of the battery containing it.
  • the M2 includes at least one of B, Mg, Al, Si, K, Ca, Ga, Ge, Se, Rb, Sr, In, Sn, Sb, Te, Sc, Ti, V, Cr, Co, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt and Au.
  • the element M2 is uniformly distributed in the bulk phase of the positive electrode active material, and can form a strong chemical bond with O in the positive electrode active material, inhibiting the release of the Na element in the positive electrode active material from the bulk phase, thereby improving the air stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • 0.01 ⁇ d/c ⁇ 0.03 which is beneficial to improving the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing the same.
  • the positive electrode active material satisfies at least one of the following conditions: 0.1 ⁇ a ⁇ 0.4, optionally 0.15 ⁇ a ⁇ 0.3; 0.1 ⁇ b ⁇ 0.35, optionally 0.15 ⁇ b ⁇ 0.35; 0.35 ⁇ c ⁇ 0.6, optionally 0.35 ⁇ c ⁇ 0.5.
  • the ratio of the sum of the contents of Ni, Fe and Mn to the content of Fe is within the above range, which is conducive to improving the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the phase of the positive electrode active material includes O3 phase
  • the space group includes R3m
  • the interlayer spacing is 0.53nm-0.55nm. Therefore, when x is within the above range, the Na content of the positive electrode active material of the formed O3 phase is high, which can improve the capacity of the battery.
  • the phase of the positive electrode active material includes a P2 phase
  • the space group includes P63/mmc
  • the interlayer spacing is 0.54nm-0.57nm.
  • the pH value of the immersion solution of the positive electrode active material is less than or equal to 13.
  • the pH value of the immersion solution of the positive electrode active material is less than or equal to 12.7. More optionally, the pH value of the immersion solution of the positive electrode active material is 11.0 ⁇ pH ⁇ 12.7.
  • the positive electrode active material satisfies at least one of the following conditions:
  • the D v 50 of the positive electrode active material is 3 ⁇ m-30 ⁇ m, and can be 5 ⁇ m-15 ⁇ m;
  • the specific surface area of the positive electrode active material is 0.1m 2 /g-5m 2 /g, and can be 0.3m 2 /g-3m 2 /g;
  • the tap density of the positive electrode active material is 1 g/cm 3 -3 g/cm 3 , and can be 1.5 g/cm 3 -2.5 g/cm 3 ;
  • the compaction density of the positive electrode active material at a pressure of 300 MPa is 3.0 g/cm 3 -4.0 g/cm 3 .
  • the conduction distance of Na ions in the positive electrode active material is small and the surface side reactions are small, which promotes the positive electrode active material to exert its gram capacity and improves the capacity retention rate of the battery containing it.
  • the second aspect of the present application provides a method for preparing the positive electrode active material according to the first aspect, comprising:
  • the precursor is calcined to obtain a positive electrode active material.
  • the positive electrode active material prepared in the present application has excellent air stability and cycle stability, and the battery containing the positive electrode active material has excellent capacity retention rate.
  • the third aspect of the present application provides another method for preparing the positive electrode active material described in the first aspect, comprising:
  • the precursor is mixed with a Na source and then calcined to obtain a positive electrode active material.
  • the positive electrode active material prepared in the present application has excellent air stability and cycle stability, and the battery containing the positive electrode active material has excellent capacity retention rate.
  • the fourth aspect of the present application provides a positive electrode plate, which includes the positive electrode active material described in the first aspect of the present application, the positive electrode active material prepared by the method described in the second aspect, or the positive electrode active material prepared by the method described in the third aspect.
  • the fifth aspect of the present application provides a battery, which comprises the positive electrode sheet described in the fourth aspect of the present application.
  • the battery has an excellent capacity retention rate.
  • a sixth aspect of the present application provides an electrical device, which includes the battery described in the fifth aspect.
  • FIG1 is a schematic structural diagram of a battery according to an embodiment of the present application.
  • FIG2 is a schematic structural diagram of a battery module according to an embodiment of the present application.
  • FIG3 is a schematic structural diagram of a battery pack according to an embodiment of the present application.
  • FIG4 is an exploded view of FIG3 ;
  • FIG5 is a schematic diagram of an embodiment of an electric device using a battery as a power source
  • FIG6 is an XRD diagram of the positive electrode active materials of Example 1 and Comparative Example 1 of the present application.
  • FIG7 is an XRD diagram of the positive electrode active materials of Example 1 and Comparative Example 2 of the present application.
  • FIG8 is a charge and discharge diagram of the positive electrode sheet of Example 1 of the present application at 1.5-4.2/4.2-1.5V;
  • FIG9 is a comparison chart of the capacity retention rates of the batteries of Example 1 and Comparative Example 4 of the present application.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
  • each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unspecified range.
  • the term "and/or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships.
  • a and/or B can represent: A exists alone, A and B exist at the same time, and B exists alone.
  • the character "/" in this article generally indicates that the associated objects before and after are in an "or" relationship.
  • Layered transition metal oxides have become one of the popular positive electrode active materials for sodium-ion batteries due to their high electrical conductivity, high energy density, large capacity and long cycle life.
  • layered transition metal oxides have the following problems: on the one hand, water vapor in the air will intrude from the surface of the layered transition metal oxide to the bulk phase, causing the structure of the layered transition metal oxide to be easily destroyed after being exposed to air for too long; on the other hand, during high-voltage charging, the oxygen coordinated with the metal in the layered transition metal oxide will also undergo an oxidation reaction, that is, lattice oxygen release will occur, causing the material structure to be destroyed; on the other hand, during high-voltage charging, cracks will be generated in the layered transition metal oxide due to the phase change accompanied by the release of sodium ions, and the electrolyte will penetrate into the material from the cracks to react and deteriorate the material structure. The destruction of the structure of the layered transition metal oxide material leads to poor stability of the material, which directly leads to a low capacity retention rate of the battery.
  • the positive electrode active material is based on NiFeMn and doped with rare earth element M1 and doping element M2 and the ratio of rare earth element M1 to Mn is controlled.
  • the rare earth element M1 has a large radius and will remain on the surface of the positive electrode active material, and form a dense and uniform doping layer on the surface of the positive electrode active material.
  • the doping layer can effectively block the intrusion of water vapor from the surface of the positive electrode active material to the bulk phase, thereby improving the structural stability of the material.
  • the doping layer can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the material, thereby improving the structural stability of the material and improving the capacity retention rate of the battery containing it;
  • the doping element M2 is distributed in the bulk phase of the positive electrode active material, and can form a strong chemical bond with O in the positive electrode active material, inhibiting the release of Na ions in the positive electrode active material from the bulk phase, and can reduce the change in the interlayer spacing of the positive electrode active material, delay the occurrence of phase change, and improve the cycle stability of the positive electrode active material.
  • the ratio d/c of the rare earth element M1 to Mn in the positive electrode active material is controlled at 0.005-0.05, which is beneficial to improving the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the positive electrode active material disclosed in the embodiment of the present application is suitable for secondary batteries, and the battery disclosed in the embodiment of the present application can be used in electrical equipment using the battery as a power source or various energy storage systems using the battery as an energy storage element.
  • Electrical equipment may include, but is not limited to, mobile phones, tablets, laptops, electric toys, electric tools, battery cars, electric cars, ships, spacecraft, and the like.
  • electric toys may include fixed or mobile electric toys, for example, game consoles, electric car toys, electric ship toys, and electric airplane toys, and the like
  • spacecraft may include airplanes, rockets, space shuttles, and spacecraft, and the like.
  • the present application provides a positive electrode active material, the positive electrode active material comprising: Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f ,
  • M1 includes rare earth elements
  • the present application includes at least the following beneficial effects: the main material of the positive electrode active material of the present application includes NiFeMn, and is doped with rare earth element M1 and doping element M2, and the above-mentioned content of Fe can improve the specific capacity of the positive electrode active material.
  • the rare earth element M1 has a large radius, and will form a dense and uniform doping layer on the surface of the positive electrode active material.
  • the doping layer can effectively block the intrusion of water vapor from the surface of the positive electrode active material to the bulk phase, and improve the structural stability of the material.
  • the doping layer can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the material, thereby improving the structural stability of the material and improving the capacity retention rate of the battery containing it.
  • the doping element M2 is distributed in the bulk phase of the positive electrode active material, and can form a strong chemical bond with O in the positive electrode active material, inhibit the release of Na ions in the positive electrode active material from the bulk phase, and can reduce the change in the interlayer spacing of the positive electrode active material, delay the occurrence of phase change, and improve the cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery.
  • the ratio d/c of the rare earth elements M1 and Mn in the positive electrode active material is within the above range, which can reduce the insufficient solid solubility between the rare earth elements and Mn, resulting in the rare earth elements agglomerating on the surface of the positive electrode active material to form a mixed phase, and at the same time reduce the probability of not being able to generate a rare earth doping layer due to insufficient rare earth elements, which is conducive to the rare earth elements forming a dense and uniform rare earth doping layer on the surface of the positive electrode active material, effectively blocking the invasion of water vapor from the surface of the positive electrode active material to the bulk phase, and can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the bulk phase, thereby improving the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the main material in the positive electrode active material includes NiFeMn, and is doped with rare earth element M1 and doping element M2, and the doping amount and d/c of each element are controlled.
  • the above characteristics work together to improve the specific capacity of the positive electrode active material.
  • x in the positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ -fFf , x can be 0.6 ⁇ x ⁇ 1.2, for example, 0.7 ⁇ x ⁇ 1.1, 0.8 ⁇ x ⁇ 1, 0.9 ⁇ x ⁇ 1.1 , 1 ⁇ x ⁇ 1.1 , etc.
  • the positive electrode active material includes the sodium element in this content, so that the battery has a higher capacity.
  • the measured sodium content x in the positive electrode active material may be less than 1.
  • the measured sodium content x in the positive electrode active material may be greater than 1 after the battery undergoes formation and circulation processes.
  • a in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f can be 0 ⁇ a ⁇ 0.5, for example, 0.001 ⁇ a ⁇ 0.5, 0.005 ⁇ a ⁇ 0.5, 0.1 ⁇ a ⁇ 0.5, 0.15 ⁇ a ⁇ 0.45, 0.2 ⁇ a ⁇ 0.4, 0.25 ⁇ a ⁇ 0.35, 0.25 ⁇ a ⁇ 0.3, etc. Therefore, the positive electrode active material includes this content of nickel, which can improve the energy density of the battery.
  • a in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f can be 0.1 ⁇ a ⁇ 0.4, for example, 0.15 ⁇ a ⁇ 0.3.
  • b in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f, b can be 0 ⁇ b ⁇ 0.4, for example, 0.001 ⁇ a ⁇ 0.4, 0.005 ⁇ a ⁇ 0.4, 0.1 ⁇ a ⁇ 0.4, 0.15 ⁇ a ⁇ 0.35, 0.2 ⁇ a ⁇ 0.35, 0.25 ⁇ a ⁇ 0.35, 0.3 ⁇ a ⁇ 0.35, etc.
  • Fe as a charge compensation metal element will be oxidized from a trivalent state to a tetravalent state.
  • the positive electrode active material includes this content of Fe, which can improve the specific capacity of the material.
  • b in the above - mentioned positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ -fFf , b may be 0.1 ⁇ b ⁇ 0.35, for example, 0.15 ⁇ b ⁇ 0.35.
  • c in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f can be 0.3 ⁇ c ⁇ 0.75, for example, 0.35 ⁇ c ⁇ 0.75, 0.4 ⁇ c ⁇ 0.7, 0.45 ⁇ c ⁇ 0.65, 0.5 ⁇ c ⁇ 0.6, 0.55 ⁇ c ⁇ 0.6, etc.
  • this content of Mn can be dissolved with the rare earth element M1 to form a uniform and dense doping layer on the surface of the positive electrode active material, thereby improving the structural stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • c in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f can be 0.35 ⁇ c ⁇ 0.6, for example, 0.35 ⁇ c ⁇ 0.5.
  • M1 in the above-mentioned positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ - fFf includes at least one of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • the M1 of this composition can form a dense and uniform doping layer on the surface of the positive electrode active material, which can effectively block the intrusion of water vapor from the surface of the positive electrode active material to the bulk phase, and improve the structural stability of the material.
  • the doping layer of this composition can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the interior of the material, thereby improving the structural stability of the material and thus improving the capacity retention rate of the battery containing it.
  • M1 adopts at least one of the above elements, which is environmentally friendly and has little pollution.
  • d in the above - mentioned positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ -fFf , d can be 0.001 ⁇ d ⁇ 0.05, for example, 0.005 ⁇ d ⁇ 0.05 , 0.01 ⁇ d ⁇ 0.05, 0.015 ⁇ d ⁇ 0.045, 0.02 ⁇ d ⁇ 0.04, 0.025 ⁇ d ⁇ 0.035, 0.03 ⁇ d ⁇ 0.035 , etc., thereby, the positive electrode active material includes the M1 element in this content, and a dense and uniform doping layer can be formed on the surface of the positive electrode active material. It effectively blocks the intrusion of water vapor from the surface of the positive electrode active material to the bulk phase, and improves the structural stability of the material.
  • the doping layer of this composition can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the material, thereby improving the structural stability of the material and thus improving the capacity retention rate of the battery containing it.
  • the contents of rare earth element M1 and Mn in the above -mentioned positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ - fFf satisfy the following relationship: 0.005 ⁇ d/c ⁇ 0.05, for example, 0.01 ⁇ d/c ⁇ 0.05, 0.015 ⁇ d/c ⁇ 0.045, 0.02 ⁇ d / c ⁇ 0.04, 0.025 ⁇ d/c ⁇ 0.035, and 0.03 ⁇ d/c ⁇ 0.035.
  • the ratio d/c of the rare earth element M1 to Mn in the positive electrode active material is within the above range, which can reduce the rare earth element agglomeration on the surface of the positive electrode active material to form a mixed phase due to insufficient solid solubility between the rare earth element and Mn, and reduce the probability of not being able to generate a rare earth doping layer due to insufficient rare earth elements, which is conducive to the rare earth element forming a dense and uniform rare earth doping layer on the surface of the positive electrode active material, effectively blocking the invasion of water vapor from the surface of the positive electrode active material to the bulk phase, and can also inhibit the precipitation of lattice oxygen and the penetration of electrolyte into the bulk phase, improve the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the content of the rare earth element M1 and Mn in the above-mentioned positive electrode active material Na x Ni a Fe b Mn c M1 d M2 e O 2+ ⁇ -f F f satisfies the following relationship 0.01 ⁇ d/c ⁇ 0.03, thereby helping to improve the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • M2 in the above - mentioned positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ -fFf includes at least one of B, Mg, Al, Si, K, Ca, Ga, Ge, Se, Rb , Sr , In, Sn, Sb, Te, Sc, Ti, V, Cr, Co, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt and Au.
  • the element M2 is uniformly distributed in its bulk phase, and M2 can form a strong chemical bond with O in the positive electrode active material, which, on the one hand, inhibits the escape of the Na element in the positive electrode active material from the bulk phase, and on the other hand, stabilizes the structure of the metal layer of the positive electrode active material, reduces the change in the interlayer spacing of the positive electrode active material, reduces the occurrence of phase change, and improves the cycle performance of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the positive electrode active material NaxNiaFebMncM1dM2eO2 + ⁇ - fF ⁇ and f in f satisfy: -0.1 ⁇ 0.1, 0 ⁇ f ⁇ 0.1, for example, -0.09 ⁇ 0.09, -0.08 ⁇ 0.08, -0.07 ⁇ 0.07, -0.06 ⁇ 0.06, -0.05 ⁇ 0.05, -0.04 ⁇ 0.04, -0.03 ⁇ 0.03, -0.02 ⁇ 0.02, -0.01 ⁇ 0.01, -0.01 ⁇ 0, 0 ⁇ 0.01, etc., 0.01 ⁇ f ⁇ 0.09, 0.02 ⁇ f ⁇ 0.08, 0.03 ⁇ f ⁇ 0.07, 0.04 ⁇ f ⁇ 0.06, 0.05 ⁇ f ⁇ 0.06, etc.
  • doping the positive electrode active material with this content of F at the oxygen position in the present application can effectively stabilize the oxygen in the positive electrode active material, thereby reducing the structural damage caused by lattice oxygen release in the positive electrode active material, improving the stability of the material, and further improving the capacity retention rate of the battery.
  • the measured oxygen content 2+ ⁇ -f in the positive electrode active material may be less than 2.
  • the ratio of the amount is within the above range, on the one hand, the amount of Na ions that can be removed from the positive electrode active material caused by too little variable valence metal component Fe is reduced, so that the positive electrode active material has an excellent specific capacity; on the other hand, the amount of Fe that migrates to the Na ion layer due to excessive Fe content in the positive electrode active material is reduced, which affects the deintercalation of Na ions, thereby improving the cycle performance of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the phase state of the positive electrode active material includes O3 phase
  • the space group includes The interlayer spacing is 0.53nm-0.55nm.
  • x can be 0.82-1.0, 0.85-0.95, 0.88-0.90, etc.
  • the interlayer spacing can be 0.53nm-0.545nm, 0.535nm-0.54nm, 0.536nm-0.539nm, etc.
  • the Na content of the positive active material of the formed O3 phase is high, and more Na ions can be released, so that the capacity of the battery is high.
  • the phase of the positive electrode active material includes a P2 phase
  • the space group includes P63/mmc
  • the interlayer spacing is 0.54nm-0.57nm.
  • x can be 0.6-0.78, 0.65-0.75, 0.68-0.7, etc.
  • the interlayer spacing can be 0.54nm-0.565nm, 0.545nm-0.56nm, 0.55nm-0.555nm, etc.
  • the interlayer spacing of the positive electrode active material of the P2 phase formed is large, which can improve the transmission rate of Na ions and maintain the integrity of the layered structure, so that the battery has excellent rate performance and cycle performance.
  • phase state, space group and interlayer spacing of the positive electrode active material in the present application can be characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, etc.
  • the characteristic peak in the range of 40.5° to 42.5° indicates that the positive electrode active material is an O3 phase
  • the space group includes The characteristic peaks in the range of 48° to 50° indicate that the positive electrode active material is a P2 phase
  • the space groups include P63/mmc.
  • the interlayer spacing of the above-mentioned O3 phase positive electrode active material can be calculated by the (003) peak position of X-ray diffraction; the interlayer spacing of the above-mentioned P2 phase positive electrode active material can be calculated by the (002) peak position of X-ray diffraction.
  • the pH value of the soaking solution of the positive electrode active material is less than or equal to 13, for example, the pH value of the soaking solution of the positive electrode active material can be 7-13, 7.2-13, 7.5-13, 8-13, 8.5-13, 9-13, 10-12.9, 10.5-12.7, 11.0-12.7, 11.2-12.5, 11.5-12.3, 11.7-12.0, etc.
  • the pH value of the soaking solution of the positive electrode active material is controlled within the above range, which can reduce the generation of gel during the slurry adjustment process and facilitate the subsequent slurry adjustment and coating of the positive electrode active material.
  • the pH value of the soaking solution of the positive electrode active material is less than or equal to 12.7, for example, the pH value of the soaking solution of the positive electrode active material is 11.0 ⁇ pH ⁇ 12.7.
  • the pH value of the immersion solution of the positive electrode active material can be measured by the following method:
  • the positive electrode active material is dispersed in pure water and soaked, and the soaking liquid is obtained by filtering, and the soaking liquid is measured and titrated with a standard hydrochloric acid solution.
  • the D v 50 of the positive electrode active material is 3 ⁇ m-30 ⁇ m, for example, the D v 50 of the positive electrode active material may be 3 ⁇ m-29 ⁇ m, 4 ⁇ m-28 ⁇ m, 5 ⁇ m-15 ⁇ m, 6 ⁇ m-14 ⁇ m, 8 ⁇ m-13 ⁇ m, 9 ⁇ m-12 ⁇ m, 10 ⁇ m-11 ⁇ m, etc. In other embodiments of the present application, the D v 50 of the positive electrode active material is 5 ⁇ m-15 ⁇ m.
  • D v 50 refers to the particle size corresponding to when the cumulative volume distribution percentage reaches 50%, for example, with reference to the standard GB/T19077-2016, and is measured using a laser particle size analyzer (eg, Malvern Master Size 3000).
  • a laser particle size analyzer eg, Malvern Master Size 3000
  • the specific surface area of the positive electrode active material is 0.1 m 2 /g-5 m 2 /g.
  • the surface area may be 0.1m2 / g-4.5m2/ g , 0.2m2 / g- 4m2 /g, 0.3m2/g-3m2 / g , 0.5m2/g-2.5m2/g, 1m2 /g-2m2 / g , 1.2m2 / g - 1.8m2 /g, etc.
  • the specific surface area of the positive electrode active material is 0.3m2 /g- 3m2 /g.
  • the specific surface area of the positive electrode active material can be tested by referring to the following method: using the American Micromeritics multi-station fully automatic specific surface area and pore analyzer GeminiVII2390, take about 7g of the sample and put it into a 9cc long tube with a bulb, degas at 200°C for 2h, and then put it into the main unit for testing to obtain the BET (specific surface area) data of the positive electrode active material.
  • the tap density of the positive electrode active material is 1g/ cm3-3g / cm3 , for example, the tap density of the positive electrode active material may be 1g/ cm3-2.8g / cm3 , 1.5g/ cm3-2.5g / cm3 , 1.7g/ cm3-2.4g / cm3 , 1.8g/ cm3-2.g / cm3 , etc. In other embodiments of the present application, the tap density of the positive electrode active material is 1.5g/ cm3-2.5g / cm3 .
  • tap density refers to the mass per unit volume of the powder in the container after being tapped under specified conditions.
  • the tap density of the positive electrode active material is determined as follows:
  • V Volume of positive electrode active material after compaction (volume of measuring cup), cm 3 .
  • the compaction density of the positive electrode active material under a pressure of 300 MPa is 3.0 g/cm 3 -4.0 g/cm 3
  • the compaction density of the positive electrode active material under a pressure of 300 MPa may be 3.0 g/cm 3 -3.9 g/cm 3 , 3.1 g/cm 3 -3.8 g/cm 3 , 3.2 g/cm 3 -3.7 g/cm 3 , 3.3 g/cm 3 -3.6 g/cm 3 , 3.4 g/cm 3 -3.5 g/cm 3 , etc.
  • the compaction density refers to the compaction density of the electrode after the material is made into an electrode.
  • Compaction density surface density / (thickness of the electrode after rolling - thickness of the current collector).
  • the compaction density of the positive electrode active material under a pressure of 300 MPa is determined as follows:
  • the conduction distance in the positive electrode active material is small and the surface side reactions are small, which promotes the positive electrode active material to exert its gram capacity and improves the capacity retention rate of the battery containing it.
  • the second aspect of the present application provides a method for preparing the positive electrode active material according to the first aspect, comprising:
  • the Na source, the Ni source, the Fe source, the Mn source, the M1 source and the M2 source are prepared according to the above positive electrode activity.
  • the material components are mixed.
  • the Na source, Ni source, Fe source, Mn source, M1 source and M2 source in the present application are conventional materials in the field, and those skilled in the art can select them according to actual conditions.
  • the Na source may include at least one of Na 2 CO 3 , NaHCO 3 , NaOH and Na 2 O 2 ;
  • the Ni source may include NiO;
  • the Fe source may include at least one of FeO, Fe 2 O 3 and Fe 3 O 4 ;
  • the Mn source may include at least one of Mn 2 O 3 , Mn 3 O 4 , MnO, and MnO 2 ;
  • the M1 source may include at least one of an oxide of M1, a salt containing M1, and other compounds;
  • the M2 source may include at least one of an oxide of M2, a salt containing M2, and other compounds.
  • At least one of the Na source, Ni source, Fe source, Mn source, M1 source and M2 source adopts at least one of its corresponding fluoride-containing salts and other compounds, such as sodium fluoride, nickel fluoride, iron fluoride, manganese fluoride, M1 fluoride (fluoride salt of M1) and M2 fluoride (fluoride salt of M2).
  • the precursor obtained above is placed in a muffle furnace and calcined in an air atmosphere, and then cooled to room temperature and mechanically crushed to obtain the positive electrode active material, wherein the calcination temperature can be 600°C-1200°C, for example, it can be 600°C-1100°C, 700°C-1000°C, 800°C-900°C, etc., and the insulation time is 10h-20h, for example, it can be 10h-19h, 11h-18h, 12h-17h, 13h-16h, 14h-15h, etc.
  • the precursor can be pre-calcined and kept warm before calcining the precursor.
  • the pre-calcination temperature can be 600°C-900°C, for example, 600°C-850°C, 650°C-800°C, 600°C-750°C, 550°C-700°C, 500°C-650°C, 550°C-600°C, etc.
  • the insulation time is 10h-20h, for example, 10h-19h, 11h-18h, 12h-17h, 13h-16h, 14h-15h, etc.
  • the solid phase method can be used to prepare the positive electrode active material with excellent air stability and cycle stability, thereby improving the capacity retention rate of the battery.
  • the third aspect of the present application provides another method for preparing the positive electrode active material described in the first aspect, comprising:
  • a Ni source, a Fe source, a Mn source, a M1 source and a M2 source are mixed with water according to the above-mentioned positive electrode active material composition to obtain a mixed solution.
  • the Ni source, Fe source, Mn source, M1 source and M2 source in the present application are conventional materials in the field, and those skilled in the art can select them according to actual conditions.
  • the Ni source may include at least one of nickel chloride, nickel sulfate, nickel nitrate and nickel oxalate
  • the Fe source may include at least one of ferric chloride, ferric sulfate, ferric nitrate and ferric oxalate
  • the Mn source may include at least one of manganese chloride, manganese sulfate, manganese nitrate and manganese oxalate
  • the M1 source may include at least one of the chloride, sulfate, nitrate and oxalate of M1
  • the M2 source may include at least one of the chloride, sulfate, nitrate, oxalate and other compounds of M2.
  • the solution obtained in step Sa is reacted with a solution containing a precipitant to obtain a precursor, wherein the solution containing a precipitant includes at least one of ammonia water, carbonic acid and oxalic acid.
  • the obtained precursor and the Na source are mixed according to the above-mentioned positive electrode active material composition, ball-milled or mechanically stirred to mix evenly, placed in a muffle furnace for calcination, and then cooled to room temperature and mechanically crushed to obtain the positive electrode active material, wherein the calcination temperature is 600°C-1200°C, for example, it can be 700°C-1100°C, 800°C-1000°C, 900°C-950°C, etc., the calcination atmosphere can be air or oxygen atmosphere, and the insulation time is 10h-20h, for example, it can be 10h-19h, 11h-18h, 12h-17h, 13h-16h, 14h-15h, etc.
  • the precursor Na source can be pre-calcined and kept warm in advance
  • the pre-calcination temperature can be 600°C-900°C, for example, 600°C-850°C, 650°C-800°C, 600°C-750°C, 550°C-700°C, 500°C-650°C, 550°C-600° C , etc.
  • the heat preservation time can be 10h-20h, for example, 10h-19h, 11h-18h, 12h-17h, 13h-16h, 14h-15h, etc.
  • the Na source can include at least one of Na2CO3 , NaHCO3 , NaOH, and Na2O2 .
  • At least one of the Na source, Ni source, Fe source, Mn source, M1 source and M2 source adopts at least one of its corresponding fluoride-containing salts and other compounds, such as sodium fluoride, nickel fluoride, iron fluoride, manganese fluoride, M1 fluoride (fluoride salt of M1) and M2 fluoride (fluoride salt of M2).
  • the coprecipitation method can be used to prepare the above-mentioned positive electrode active material with excellent air stability and cycle stability, thereby improving the capacity retention rate of the battery.
  • the fourth aspect of the present application provides a positive electrode plate, which includes the positive electrode active material described in the first aspect of the present application, the positive electrode active material prepared by the method described in the second aspect, or the positive electrode active material prepared by the method described in the third aspect.
  • the positive electrode sheet generally includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode current collector may be a conventional metal foil or a composite current collector (a metal material may be disposed on a polymer substrate to form a composite current collector).
  • the positive electrode current collector may include at least one of copper foil, aluminum foil, nickel foil, stainless steel foil, stainless steel mesh, and carbon-coated aluminum foil.
  • the positive electrode active material includes the positive electrode active material described in the first aspect of the present application, the positive electrode active material prepared by the method described in the second aspect, or the positive electrode active material prepared by the method described in the third aspect.
  • the positive electrode active material layer may also optionally include a conductive agent and a binder.
  • the conductive agent is used to improve the conductivity of the positive electrode active material layer
  • the binder is used to firmly bind the positive electrode active material and the binder to the positive electrode current collector.
  • the present application does not specifically limit the types of the conductive agent and the binder, and they can be selected according to actual needs.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers;
  • the binder may include at least one of styrene-butadiene rubber (SBR), water-based acrylic resin, carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA) and polyvinyl alcohol (PVA).
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • EVA ethylene-vinyl acetate copolymer
  • PVA polyvinyl alcohol
  • the fifth aspect of the present application provides a battery, which comprises the positive electrode sheet described in the fourth aspect of the present application.
  • the battery has an excellent capacity retention rate.
  • a battery is a battery that can be used again by recharging the active materials after discharge.
  • the battery proposed in this application is a sodium ion battery.
  • a battery includes a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte.
  • active ions are embedded and released back and forth between the positive electrode sheet and the negative electrode sheet.
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet to play a role of isolation.
  • the electrolyte plays a role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the negative electrode plate generally includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, wherein the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode current collector may be a conventional metal foil or a composite current collector (for example, a metal material may be disposed on a polymer substrate to form a composite current collector).
  • the negative electrode current collector may be a copper foil.
  • the negative electrode active material is not limited, and active materials known in the art that can be used for the negative electrode of a sodium ion battery can be used, and those skilled in the art can select according to actual needs.
  • the negative electrode active material can include but is not limited to at least one of sodium metal, carbon material, alloy material, transition metal oxide and/or sulfide, phosphorus-based material, and titanate material.
  • the carbon material may include at least one of hard carbon, soft carbon, amorphous carbon, and nanostructured carbon materials
  • the alloy material may include an alloy material formed by at least one of Si, Ge, Sn, Pb, and Sb; the general formula of the transition metal oxide and sulfide is M x N y , wherein M includes at least one of Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb, and V, and N includes O or S;
  • the phosphorus-based material may include at least one of red phosphorus, white phosphorus, and black phosphorus;
  • the titanate material may include at least one of Na 2 Ti 3 O 7 , Na 2 Ti 6 O 13 , Na 4 Ti 5 O 12 , Li 4 Ti 5 O 12 , and NaTi 2 (PO 4 ) 3. All of these materials can be obtained through commercial channels.
  • the negative electrode active material layer may also optionally include a binder and a conductive agent.
  • the conductive agent is used to improve the conductivity of the negative electrode active material layer
  • the binder is used to firmly bind the negative electrode active material and the binder to the negative electrode current collector.
  • the present application does not specifically limit the types of the conductive agent and the binder, and they can be selected according to actual needs.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the binder may include at least one of styrene butadiene rubber (SBR), styrene butadiene rubber (SBCs), water-based acrylic resin and carboxymethyl cellulose (CMC).
  • SBR styrene butadiene rubber
  • SBCs styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the negative electrode active material layer may also optionally include a thickener, such as carboxymethyl cellulose (CMC).
  • a thickener such as carboxymethyl cellulose (CMC).
  • CMC carboxymethyl cellulose
  • the present application is not limited thereto, and the present application may also use other materials that can be used as thickeners for negative electrode sheets of sodium ion batteries.
  • the electrolyte may include an electrolyte salt and a solvent.
  • the electrolyte sodium salt may include at least one of sodium hexafluorophosphate, sodium difluorooxalatoborate, sodium tetrafluoroborate, sodium bisoxalatoborate, sodium perchlorate, sodium hexafluoroarsenate, sodium bis(fluorosulfonyl)imide, sodium trifluoromethylsulfonate, and sodium bis(trifluoromethylsulfonyl)imide.
  • the solvent may include ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), At least one of butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS) and diethyl sulfone (ESE).
  • the electrolyte further includes additives, such as additives that may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high temperature performance, and additives that improve battery low temperature performance.
  • additives such as additives that may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high temperature performance, and additives that improve battery low temperature performance.
  • the present application has no special restrictions and any known porous structure isolation membrane with electrochemical stability and mechanical stability can be selected according to actual needs.
  • it can include a single-layer or multi-layer film containing at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • FIG1 is a square-structured battery 1 as an example.
  • the battery may include an outer packaging for packaging the positive electrode sheet, the negative electrode sheet, and the electrolyte.
  • the outer package may include a shell and a cover plate.
  • the shell may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell has an opening connected to the receiving cavity, and the cover plate can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the separator can be wound or laminated to form an electrode assembly.
  • the electrode assembly is packaged in the receiving cavity.
  • the number of electrode assemblies contained in the battery can include one or more, which can be adjusted according to demand.
  • the outer packaging of the battery may include a hard shell, such as a hard plastic shell, an aluminum shell, or a steel shell.
  • the outer packaging of the battery may also include a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, such as at least one of polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
  • the batteries may be assembled into a battery module.
  • the battery module may contain multiple batteries, and the specific number may be adjusted according to the application and capacity of the battery module.
  • FIG2 is a battery module 2 as an example.
  • a plurality of batteries 1 may be arranged in sequence along the length direction of the battery module 2. Of course, they may also be arranged in any other manner. Further, the plurality of batteries 1 may be fixed by fasteners.
  • the battery module 2 may also include a housing having a storage space, in which a plurality of batteries 1 are stored.
  • the battery modules may be assembled into a battery pack, and the number of battery modules contained in the battery pack may be adjusted according to the application and capacity of the battery pack.
  • the battery pack 3 may include a battery box and a plurality of battery modules 2 disposed in the battery box.
  • the battery box includes an upper box body 4 and a lower box body 5, and the upper box body 4 can be covered on the lower box body 5 to form a closed space for accommodating the battery modules 2.
  • the plurality of battery modules 2 can be arranged in the battery box in any manner.
  • the sixth aspect of the present application provides an electrical device, which includes the battery described in the fifth aspect.
  • the battery can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device.
  • the electrical device may include, but is not limited to, mobile devices (such as mobile phones, laptops), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks), electric trains, ships and satellites, and energy storage systems.
  • Fig. 5 is an example of an electric device, which includes a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • the electric device may include a mobile phone, a tablet computer, and a notebook computer.
  • the electric device is usually required to be thin and light, and a battery may be used as a power source.
  • the prepared NaNi 0.2 Fe 0.2 Mn 0.5 La 0.02 Cu 0.08 O 2 , conductive agent carbon black, binder polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) were stirred and mixed uniformly at a weight ratio of 60:5:5:30 to obtain a positive electrode slurry; the positive electrode slurry was uniformly coated on a positive electrode aluminum foil current collector, and the positive electrode sheet was obtained after drying, cold pressing, and slitting.
  • the negative electrode plate is made of metallic sodium.
  • Glass fiber is used as the isolation membrane.
  • the positive electrode sheet, the separator, and the negative electrode sheet are stacked in order, so that the separator is between the positive and negative electrode sheets to play an isolating role, and then they are wound to obtain an electrode assembly; the electrode assembly is placed in an outer package, and the prepared electrolyte is injected into the dried secondary battery. After vacuum packaging, standing, formation, and shaping processes, a secondary battery is obtained.
  • the secondary batteries containing the positive electrode active materials of Examples 2-24 and Comparative Examples 1-4 are the same as Example 1 except for the different parameters (see Table 1).
  • compositions of the positive electrode active materials in the batteries of Examples 1-24 and Comparative Examples 1-4 of the present application are shown in Table 1.
  • the D v 50, specific surface area, tap density, compaction density under a pressure of 300 MPa, pH value of the immersion solution, phase state, space group and interlayer spacing of the positive electrode active materials in Examples 1-24 and Comparative Examples 1-4, and the capacity and capacity retention rate of the obtained sodium ion batteries were characterized.
  • the characterization results are shown in Table 2.
  • the wavelength of the ray is The characteristic peaks in the scanning 2 ⁇ angle range of 40.5° to 42.5° indicate that the positive electrode active material is O3 phase, and the space groups include The characteristic peaks scanning the 2 ⁇ angle in the range of 48° to 50° indicate that the positive electrode active material is a P2 phase, and the space group includes P63/mmc.
  • Determination of tap density Load the weighed positive electrode active material into the measuring cylinder of the tapping device and fix the measuring cylinder on the support. Turn the cam, and the directional rod drives the support to slide up and down and hit the anvil. Vibrate 250 ⁇ 15 times per minute for 12 minutes. Determine the volume of the positive electrode active material in the measuring cylinder. The ratio of the mass of the positive electrode active material to the volume is the tap density of the positive electrode active material.
  • V Volume of positive electrode active material after compaction (volume of measuring cup), cm 3 .
  • Determination of pH value of the soaking solution of the positive electrode active material disperse the positive electrode active material in pure water and soak it, filter to obtain the soaking solution, and measure the soaking solution and titrate it with standard hydrochloric acid solution.
  • M2 actual weight of the pole piece
  • M1 average weight of current collector
  • Example 1 at 25°C, the secondary battery was charged at a constant current rate of 0.1C to a charge cut-off voltage of 4.2V, then discharged at 0.1C to 1.5V, left standing for 5 minutes, and then discharged at a constant current rate of 0.5C to a discharge cut-off voltage of 2.8V, left standing for 5 minutes, and the battery discharge capacity C 0 was recorded at this time. According to this method, the battery was charged and discharged for 500 cycles, and the battery discharge capacity after 500 cycles was recorded as C 1 .
  • the cycle capacity retention rate of the secondary battery C 1 /C 0 ⁇ 100%.
  • the XRD patterns of the positive electrode active materials of Example 1, Comparative Example 1 and Comparative Example 2 are shown in Figures 6 and 7.
  • the ratio d/c of the rare earth element M1 to Mn in the positive electrode active material of Comparative Example 1 is 0.004, which is less than 0.005, and the peak between 10-20 of the positive electrode active material is not obvious, while the impurity peak between 30-40 is more obvious. It can be seen that too little rare earth element is not conducive to improving the air stability and cycle stability of the positive electrode active material; compared with Example 1, the ratio d/c of the rare earth element M1 to Mn in the positive electrode active material of Comparative Example 2 is 0.06, which is greater than 0.05, and the positive electrode active material has obvious impurity peaks. It can be seen that there are too many rare earth elements and the solid solubility between the rare earth elements and Mn is insufficient, which causes the rare earth elements to agglomerate on the surface of the positive electrode active material to form an impurity phase.
  • FIG8 is a charge and discharge curve of the sodium ion battery prepared in Example 1 at 0.1C in the first cycle, and it can be seen that the operating voltage range of the battery is 1.5V-4.2V.
  • Example 1 A comparison chart of the capacity retention rates of Example 1 and Comparative Example 4 is shown in FIG9 . It can be seen that the capacity retention rate of Example 1 of the present application is significantly better than that of Comparative Example 4.
  • NiFeMn is used as the main material and is doped with rare earth element M1 and doping element M2 and the ratio of rare earth element M1 to Mn is controlled, which can improve the air stability and cycle stability of the positive electrode active material, thereby improving the capacity retention rate of the battery containing it.
  • the values of d/c in Comparative Examples 1 and 2 are not within the scope of the embodiments of the present application, and the values of the content c of Mn in Comparative Examples 3 and 4 are not within the scope of the embodiments of the present application, and the capacity retention rate and capacity of the battery containing it are significantly reduced.

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Abstract

本申请公开了一种正极活性材料及其制备方法、正极极片、电池和用电设备，所述正极活性材料包括： NaxNiaFebMncM1dM2eO2+δ-fFf 其中，M1包括稀土元素，M2包括第ⅠA族元素、第ⅡA族元素、第ⅢA族元素、第ⅣA族元素、第ⅤA族元素、第ⅥA族元素和过渡元素中的至少一种，0.6≤x≤1.2，0＜a≤0.5，0＜b≤0.4，0.3≤c≤0.75，0.001≤d≤0.05，0≤e≤0.3，-0.1≤δ≤0.1，0≤f≤0.1，0.005≤d/c≤0.05，a+b+c+d+e＝1。

Description

正极活性材料及其制备方法、正极极片、电池和用电设备 技术领域
本申请涉及二次电池技术领域，具体涉及一种正极活性材料及其制备方法、正极极片、电池和用电设备。
背景技术
二次电池不仅被应用于水力、火力、风力和太阳能电站等储能电源系统，而且还被广泛应用于电动自行车、电动摩托车、电动汽车等电动交通工具，以及军事装备和航空航天等多个领域。
钠离子电池是二次电池的一种，层状过渡金属氧化物是钠离子电池常用的正极活性材料。然而，现有的含有层状过渡金属氧化物钠离子电池的容量保持率较低。
发明内容
鉴于背景技术中存在的技术问题，本申请提供一种正极活性材料，旨在解决含有其的电池容量保持率低的问题。
为了实现上述目的，本申请的第一方面提供了一种正极活性材料，所述正极活性材料包括：
NaxNiaFebMncM1dM2eO2+δ-fFf，
其中，M1包括稀土元素，M2包括第ⅠA族元素、第ⅡA族元素、第ⅢA族元素、第ⅣA族元素、第ⅤA族元素、第ⅥA族元素和过渡元素中的至少一种，0.6≤x≤1.2，0＜a≤0.5，0＜b≤0.4，0.3≤c≤0.75，0.001≤d≤0.05，0≤e≤0.3，-0.1≤δ≤0.1，0≤f≤0.1，0.005≤d/c≤0.05，a+b+c+d+e＝1。
本申请至少包括如下所述的有益效果：本申请的正极活性材料中主体材料包括NiFeMn，并且掺杂稀土元素M1和掺杂元素M2，上述含量的Fe可以提高材料的比容量。稀土元素M1的半径大，会在正极活性材料的表面形成致密均匀的掺杂层，掺杂层可以有效地阻挡水汽从正极活性材料表面向体相的侵入，提高材料的结构稳定性。在高压充电过程中，掺杂层还可以抑制晶格氧的析出和电解液渗入材料内部，提高材料的结构稳定性，从而提升含有其的电池的容量保持率。掺杂元素M2分布在正极活性材料的体相，可以与正极活性材料中的O形成强的化学键，抑制正极活性材料中的Na离子从体相的脱出，并且可以降低正极活性材料的层间距变化，推迟相变发生，提升了正极活性材料的循环稳定性，从而提升电池的容量保持率。此外，正极活性材料中稀土元素M1与Mn的比例d/c在上述范围内，有利于提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，所述稀土元素包括La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、 Tm、Yb和Lu中的至少一种。由此，M1采用上述稀土元素中的至少一种，可以在正极活性材料的表面形成致密均匀的掺杂层，降低了正极活性材料相变的发生概率，提升了正极活性材料的循环性能，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，所述M2包括B、Mg、Al、Si、K、Ca、Ga、Ge、Se、Rb、Sr、In、Sn、Sb、Te、Sc、Ti、V、Cr、Co、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt和Au的至少一种。由此，元素M2均匀分布在正极活性材料的体相，可以与正极活性材料中的O形成强的化学键，抑制正极活性材料中的Na元素从体相的脱出，提升了正极活性材料的空气稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，0.01≤d/c≤0.03，由此，有利于提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，所述正极活性材料满足以下条件中的至少之一：0.1≤a≤0.4，可选为0.15≤a≤0.3；0.1≤b≤0.35，可选为0.15≤b≤0.35；0.35≤c≤0.6，可选为0.35≤c≤0.5。
在本申请一些实施方式中，1.75≤(a+b+c)/b≤9.5，可选地，2≤(a+b+c)/b≤9.5，更可选地，2≤(a+b+c)/b≤6.3。由此，正极活性材料中，Ni、Fe和Mn的含量之和与Fe含量的比例在上述范围内，有利于提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，0.8＜x≤1.0，所述正极活性材料的相态包括O3相，空间群包括R3m，层间距为0.53nm-0.55nm。由此，x在上述范围内，形成的O3相的正极活性材料Na含量高，可以提高电池的容量。
在本申请一些实施方式中，0.6≤x≤0.8，所述正极活性材料的相态包括P2相，空间群包括P63/mmc，层间距为0.54nm-0.57nm。由此，x在上述范围内，形成的P2相的正极活性材料的层间距大，可以提高电池的倍率性能和循环性能。
在本申请的一些实施方式中，所述正极活性材料的浸泡液的pH值小于或等于13，可选地，所述正极活性材料的浸泡液的pH值小于或等于12.7，更可选地，所述正极活性材料的浸泡液的pH值为11.0≤pH≤12.7。
在本申请一些实施方式中，所述正极活性材料满足以下条件中的至少之一：
所述正极活性材料的Dv50为3μm-30μm，可选为5μm-15μm；
所述正极活性材料的比表面积为0.1m2/g-5m2/g，可选为0.3m2/g-3m2/g；
所述正极活性材料的振实密度为1g/cm3-3g/cm3，可选为1.5g/cm3-2.5g/cm3；
所述正极活性材料在300MPa压力下的压实密度为3.0g/cm3-4.0g/cm3。
由此，当正极活性材料的Dv50、比表面积、振实密度和300MPa压力下的压实密度中的至少之一在上述范围时，正极活性材料内Na离子的传导距离小、表面副反应少，促进了正极活性材料发挥其克容量，提升了含有其的电池的容量保持率。
本申请第二方面提供了一种制备第一方面所述的正极活性材料的方法，包括：
将Na源、Ni源、Fe源、Mn源、M1源和M2源混合得到前驱体；
将所述前驱体进行煅烧，得到正极活性材料。
由此，本申请制备的正极活性材料，具有优异的空气稳定性和循环稳定性，含有其的电池具有优异的容量保持率。
本申请第三方面提供了另一种制备第一方面所述的正极活性材料的方法，包括：
将Ni源、Fe源、Mn源、M1源和M2源与水混合得到混合溶液；
将所述溶液与沉淀剂反应得到前驱体；
将前驱体与Na源混合后进行煅烧，得到正极活性材料。
由此，本申请制备的正极活性材料，正极活性材料具有优异的空气稳定性和循环稳定性，含有其的电池具有优异的容量保持率。
本申请第四方面提供了一种正极极片，其包括本申请第一方面所述的正极活性材料、第二方面所述的方法制备的正极活性材料或第三方面所述的方法制备的正极活性材料。
本申请第五方面提供了一种电池，其包括本申请第四方面的所述的正极极片。由此，该电池具有优异的容量保持率。
本申请第六方面提供了一种用电设备，其包括第五方面所述的电池。
本申请的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。
附图说明
通过阅读对下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本申请的限制。而且在全部附图中，用相同的附图标号表示相同的部件。在附图中：
图1是本申请一实施方式的电池的结构示意图；
图2是本申请一实施方式的电池模块的结构示意图；
图3是本申请一实施方式的电池包的结构示意图；
图4是图3的分解图；
图5是电池用作电源的用电设备的一实施方式的示意图；
图6是本申请实施例1和对比例1的正极活性材料的XRD图；
图7是本申请实施例1和对比例2的正极活性材料的XRD图；
图8是本申请实施例1的正极极片在1.5-4.2/4.2-1.5V的充电和放电图；
图9是本申请实施例1和对比例4的电池的容量保持率对比图。
附图标记说明：
1：二次电池；2：电池模块；3：电池包；4：上箱体；5：下箱体。
具体实施方式
下面对本申请技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本申请的技术方案，因此只作为示例，而不能以此来限制本申请的保护范围。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
为了简明，本文仅具体地公开了一些数值范围。然而，任意下限可以与任意上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，每个单独公开的点或单个数值自身可以作为下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请的说明书和权利要求书及上述附图说明中的术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的包含。
随着电动汽车与可充电移动设备的技术发展和需求提升，二次电池作为新能源领域的代表，与其相关的研究工作也迅猛发展。钠离子电池相比于传统的锂离子电池具有强劲的价格优势，在大规模储电系统中具有广泛的应用前景。
层状过渡金属氧化物由于高电导率、高能量密度、较大的容量和较长的循环寿命，所以成为热门的钠离子电池正极活性材料之一。
然而现有的层状过渡金属氧化物存在以下问题：一方面空气中水汽会从层状过渡金属氧化物表面向体相侵入，导致层状过渡金属氧化物接触空气过久后其结构容易被破坏；再一方面，在高压充电时，层状过渡金属氧化物中与金属配位的氧也会发生氧化反应，即发生晶格释氧，导致材料结构被破坏；另一方面，在高压充电时，层状过渡金属氧化物中由于钠离子的脱出伴随的相变会产生裂缝，电解液会从裂缝中渗入到材料内部发生反应，恶化材料的结构。层状过渡金属氧化物材料结构的破坏，导致材料的稳定性变差，从而直接导致电池的容量保持率较低。
在本申请中，正极活性材料以NiFeMn为主体材料且掺杂稀土元素M1和掺杂元素M2并控制稀土元素M1和Mn的比例，一方面，稀土元素M1的半径大，会留在正极活性材料的表面，并在正极活性材料的表面形成致密均匀的掺杂层，掺杂层可以有效地阻挡水汽从正极活性材料表面向体相的侵入，提高材料的结构稳定性。此外，在高压充电过程中，掺杂层还可以抑制晶格氧的析出和电解液渗入材料内部，提高材料的结构稳定性，从而提升含有其的电池的容量保持率；另一方面，掺杂元素M2分布在正极活性材料的体相，可以与正极活性材料中的O形成强的化学键，抑制正极活性材料中的Na离子从体相的脱出，并且可以降低正极活性材料的层间距变化，推迟相变发生，提升正极活性材料的循环稳定性。另外，本申请中正极活性材料中稀土元素M1与Mn的比例d/c控制在0.005-0.05，有利于提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
本申请实施例公开的正极活性材料适用于二次电池，并且本申请实施例公开的电池可以用于使用电池作为电源的用电设备或者使用电池作为储能元件的各种储能系统。用电设备可以包括但不限于手机、平板、笔记本电脑、电动玩具、电动工具、电瓶车、电动汽车、轮船、航天器等等。其中，电动玩具可以包括固定式或移动式的电动玩具，例如，游戏机、电动汽车玩具、电动轮船玩具和电动飞机玩具等等，航天器可以包括飞机、火箭、航天飞机和宇宙飞船等等。
本申请第一方面提出了一种正极活性材料，所述正极活性材料包括：
NaxNiaFebMncM1dM2eO2+δ-fFf，
其中，M1包括稀土元素，M2包括第ⅠA族元素、第ⅡA族元素、第ⅢA族元素、第ⅣA族元素、第ⅤA族元素、第ⅥA族元素和过渡元素中的至少一种，0.6≤x≤1.2，0＜a≤0.5，0＜b≤0.4，0.3≤c≤0.75，0.001≤d≤0.05，0≤e≤0.3，-0.1≤δ≤0.1，0≤f≤0.1，0.005≤d/c≤0.05，a+b+c+d+e＝1。
本申请至少包括如下所述的有益效果：本申请的正极活性材料中主体材料包括NiFeMn，并且掺杂稀土元素M1和掺杂元素M2，上述含量的Fe可以提高正极活性材料的比容量。稀土元素M1的半径大，会在正极活性材料的表面形成致密均匀的掺杂层，掺杂层可以有效地阻挡水汽从正极活性材料表面向体相的侵入，提高材料的结构稳定性。在高压充电过程中，掺杂层还可以抑制晶格氧的析出和电解液的渗入材料内部，提高材料的结构稳定性，从而提升含有其的电池的容量保持率。掺杂元素M2分布在正极活性材料的体相，可以与正极活性材料中的O形成强的化学键，抑制正极活性材料中的Na离子从体相的脱出，并且可以降低正极活性材料的层间距变化，推迟相变发生，提升了正极活性材料的循环稳定性，从而提升电池的容量保持率。
此外，正极活性材料中稀土元素M1与Mn的比例d/c在上述范围内，可以降低稀土元素与Mn之间固溶度不足而导致稀土元素在正极活性材料表面团聚而生成杂相，同时减小因稀土元素不足而无法生成稀土掺杂层的概率，有利于稀土元素在正极活性材料的表面形成致密均匀的稀土掺杂层，有效地阻挡水汽从正极活性材料的表面向体相的侵入，也可以抑制晶格氧的析出和电解液渗入到体相，提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
综上，正极活性材料中主体材料包括NiFeMn，并且掺杂稀土元素M1和掺杂元素M2，且控制了各元素的掺杂量及d/c，上述特征综合而言，共同发挥作用，可以提高正极活性材料的比容量。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中x可以取0.6≤x≤1.2，例如0.7≤x≤1.1，0.8≤x≤1，0.9≤x≤1.1，1≤x≤1.1等。由此，该正极活性材料中包括该含量的钠元素，使得电池具有较高的容量。
需要说明的是，在正极极片、电池或者用电装置，由于电池经过化成和循环等过程，钠离子会有消耗，因此会出现测出的正极活性材料中钠元素含量x小于1的情况。同时若正极极片和负极极片采用了补钠剂，电池经过化成和循环等过程后，会出现测出的正极活性材料中钠元素含量x大于1的情况。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中a可以取0＜a≤0.5，例如0.001≤a≤0.5，0.005≤a≤0.5，0.1≤a≤0.5，0.15≤a≤0.45，0.2≤a≤0.4，0.25≤a≤0.35，0.25≤a≤0.3等。由此，该正极活性材料中包括该含量的镍，可以提高电池的能量密度。在本申请另一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中a可以取0.1≤a≤0.4，例如0.15≤a≤0.3。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中b可以取0＜b≤0.4，例如0.001≤a≤0.4，0.005≤a≤0.4，0.1≤a≤0.4，0.15≤a≤0.35，0.2≤a≤0.35，0.25≤a≤0.35，0.3≤a≤0.35等。由此，在Na离子从材料脱出过程中，Fe作为电荷补偿金属元素会从三价态氧化至四价态。在Na离子重新嵌入到材料时，Fe又会从四价态还原至三价态，该正极活性材料中包括该含量的Fe，可以提高材料的比容量。在本申请另一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中b可以取0.1≤b≤0.35，例如0.15≤b≤0.35。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中c可以取0.3≤c≤0.75，例如0.35≤c≤0.75，0.4≤c≤0.7，0.45≤c≤0.65，0.5≤c≤0.6，0.55≤c≤0.6等。由此，该含量的Mn可以与稀土元素M1发生固溶在正极活性材料表面形成均匀致密的掺杂层，提高正极活性材料的结构稳定性，从而提升含有其的电池的容量保持率。在本申请另一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中c可以取0.35≤c≤0.6，例如为0.35≤c≤0.5。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中M1包括La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的至少一种。由此，该组成的M1可以在正极活性材料的表面形成致密均匀的掺杂层，可以有效地阻挡水汽从正极活性材料表面向体相的侵入，提高材料的结构稳定性。同时在高压充电过程中，该组成的掺杂层还可以抑制晶格氧的析出和电解液渗入材料内部，提高材料的结构稳定性，从而提升含有其的电池的容量保持率。
此外，M1采用上述元素中的至少一种，环境友好，污染小。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中d可以取0.001≤d≤0.05，例如0.005≤d≤0.05，0.01≤d≤0.05，0.015≤d≤0.045，0.02≤d≤0.04，0.025≤d≤0.035，0.03≤d≤0.035等，由此，该正极活性材料中包括该含量的M1元素，可以在正极活性材料表面形成致密均匀的掺杂层， 有效地阻挡水汽从正极活性材料表面向体相的侵入，提高材料的结构稳定性。同时在高压充电过程中，该组成的掺杂层还可以抑制晶格氧的析出和电解液渗入材料内部，提高材料的结构稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中稀土元素M1与Mn含量满足以下关系式：0.005≤d/c≤0.05，例如0.01≤d/c≤0.05，0.015≤d/c≤0.045，0.02≤d/c≤0.04，0.025≤d/c≤0.035，0.03≤d/c≤0.035。正极活性材料中稀土元素M1与Mn的比例d/c在上述范围内，可以降低稀土元素与Mn之间固溶度不足而导致稀土元素在正极活性材料表面团聚而生成杂相，同时减小因稀土元素不足而无法生成稀土掺杂层的概率，有利于稀土元素在正极活性材料的表面形成致密均匀的稀土掺杂层，有效地阻挡水汽从正极活性材料的表面向体相的侵入，也可以抑制晶格氧的析出和电解液渗入到体相，提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。在本申请另一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中稀土元素M1与Mn含量满足以下关系式0.01≤d/c≤0.03，由此，有利于提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中M2包括B、Mg、Al、Si、K、Ca、Ga、Ge、Se、Rb、Sr、In、Sn、Sb、Te、Sc、Ti、V、Cr、Co、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt和Au的至少一种。具体的，在正极活性材料中，元素M2均匀分布在其体相，且M2可以与正极活性材料中的O形成强的化学键，该化学键一方面抑制了正极活性材料中的Na元素从体相的脱出，另一方面稳定了正极活性材料的金属层的结构，减小了正极活性材料层间距的变化，降低了相变的发生，提升了正极活性材料的循环性能，从而提升含有其的电池的容量保持率。
在一些实施方式中，上述的正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中δ和f满足：-0.1≤δ≤0.1，0≤f≤0.1，例如-0.09≤δ≤0.09，-0.08≤δ≤0.08，-0.07≤δ≤0.07，-0.06≤δ≤0.06，-0.05≤δ≤0.05，-0.04≤δ≤0.04，-0.03≤δ≤0.03，-0.02≤δ≤0.02，-0.01≤δ≤0.01，-0.01≤δ≤0，0≤δ≤0.01等，0.01≤f≤0.09，0.02≤f≤0.08，0.03≤f≤0.07，0.04≤f≤0.06，0.05≤f≤0.06等。具体的，本申请的正极活性材料中氧位掺杂该含量的F，可以有效稳定正极活性材料中的氧，从而降低正极活性材料中晶格释氧导致的结构破坏，提高材料的稳定性，进而提高电池的容量保持率。
需要说明的是，在正极极片、电池或者用电装置，由于电池经过循环等过程，正极活性材料中氧元素有损失，因此会出现测出的正极活性材料中氧元素含量2+δ-f小于2的情况。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中1.75≤(a+b+c)/b≤9.5，例如1.8≤(a+b+c)/b≤9.5，1.9≤(a+b+c)/b≤9.4，2≤(a+b+c)/b≤9.3，2.1≤(a+b+c)/b≤9.2，2.2≤(a+b+c)/b≤9.1，2.3≤(a+b+c)/b≤9，2.5≤(a+b+c)/b≤8.5，3≤(a+b+c)/b≤8，3.5≤(a+b+c)/b≤7.5，4≤(a+b+c)/b≤7，4.5≤(a+b+c)/b≤6.5，5≤(a+b+c)/b≤6，5≤(a+b+c)/b≤5.5等。具体的控制上述正极活性材料中Ni、Fe和Mn的含量之和与Fe含 量的比例在上述范围内，一方面降低了可变价金属组分Fe过少引起的正极活性材料中可脱出的Na离子变少，使正极活性材料具有优异的比容量；另一方面，减小了正极活性材料中Fe含量过多引起的大量Fe迁移到Na离子层而影响Na离子的脱嵌，提升正极活性材料的循环性能，从而提升含有其的电池的容量保持率。
在本申请一些实施方式中，上述正极活性材料NaxNiaFebMncM1dM2eO2+δ-fFf中0.8＜x≤1.0，所述正极活性材料的相态包括O3相，空间群包括层间距为0.53nm-0.55nm。例如，x可以是0.82-1.0，0.85-0.95，0.88-0.90等，层间距可以是0.53nm-0.545nm，0.535nm-0.54nm，0.536nm-0.539nm等。具体的，x在上述范围内，形成的O3相的正极活性材料Na含量高，能够脱出更多的Na离子，使得电池的容量高。
在本申请一些实施方式中，0.6≤x≤0.8，所述正极活性材料的相态包括P2相，空间群包括P63/mmc，层间距为0.54nm-0.57nm。例如，x可以是0.6-0.78，0.65-0.75，0.68-0.7等，层间距可以是0.54nm-0.565nm，0.545nm-0.56nm，0.55nm-0.555nm等，具体的，x在上述范围内，形成的P2相的正极活性材料的层间距大，能够提升Na离子的传输速率，保持层状结构的完整性，使得电池具有优异的倍率性能和循环性能。
需要说明的是，本申请中的正极活性材料的相态、空间群和层间距的表征方法可以为X射线衍射、扫描电子显微镜、透射电子显微镜等。具体的，X射线衍射图谱中，40.5°至42.5°范围内的特征峰表示正极活性材料为O3相，空间群包括48°至50°范围内的特征峰表示正极活性材料为P2相，空间群包括P63/mmc，上述O3相的正极活性材料的层间距，可以通过X射线衍射的(003)峰位置计算得到；上述P2相的正极活性材料的层间距，可以通过X射线衍射的(002)峰位置计算得到。
在本申请一些实施方式中，所述正极活性材料的浸泡液的pH值小于或等于13，例如正极活性材料浸泡液的pH值可以是7-13，7.2-13，7.5-13，8-13，8.5-13，9-13，10-12.9，10.5-12.7，11.0-12.7，11.2-12.5，11.5-12.3，11.7-12.0等，正极活性材料浸泡液的pH值控制在上述范围内，可以降低在调浆过程中产生凝胶，易于后续正极活性材料的调浆涂布。在本申请另一些实施方式中，所述正极活性材料的浸泡液的pH值小于或等于12.7，例如所述正极活性材料的浸泡液的pH值为11.0≤pH≤12.7。
具体的，正极活性材料的浸泡液的pH值可以采用如下方法测得：
将正极活性材料分散到纯水中浸泡，过滤得到浸泡液，量取浸泡液用标准盐酸溶液滴定。
在本申请一些实施方式中，所述正极活性材料的Dv50为3μm-30μm，例如，正极活性材料的Dv50可以是3μm-29μm，4μm-28μm，5μm-15μm，6μm-14μm，8μm-13μm，9μm-12μm，10μm-11μm等。在本申请的另一些实施方式中，所述正极活性材料的Dv50为5μm-15μm。
本申请中，Dv50是指累计体积分布百分数达到50％时所对应的粒径，例如参照标准GB/T19077-2016，使用激光粒度分析仪(例如Malvern Master Size 3000)进行测定。
在本申请一些实施方式中，所述正极活性材料的比表面积为0.1m2/g-5m2/g，例如正极活性材料的比 表面积可以是0.1m2/g-4.5m2/g，0.2m2/g-4m2/g，0.3m2/g-3m2/g，0.5m2/g-2.5m2/g，1m2/g-2m2/g，1.2m2/g-1.8m2/g等。在本申请的另一些实施方式中，所述正极活性材料的比表面积为0.3m2/g-3m2/g。
本申请中，正极活性材料的比表面积可以参照如下方法测试得到：使用美国麦克多站式全自动比表面积与孔隙分析仪GeminiVII2390，取约7g左右的样品放入9cc带球泡的长管中，200℃脱气2h，随后放入主机测试得到正极活性材料的BET(比表面积)数据。
在本申请一些实施方式中，所述正极活性材料的振实密度为1g/cm3-3g/cm3，例如正极活性材料的振实密度可以是1g/cm3-2.8g/cm3，1.5g/cm3-2.5g/cm3，1.7g/cm3-2.4g/cm3，1.8g/cm3-2.g/cm3等。在本申请另一些实施方式中，所述正极活性材料的振实密度为1.5g/cm3-2.5g/cm3。
本申请中，振实密度是指在规定条件下容器中的粉末经振实后所测得的单位容积的质量。正极活性材料的振实密度的测定方法如下：
将称量好的正极活性材料装入振实装置量筒，将量筒固定在支座上。转动凸轮，定向杆带动支座上、下滑动，并撞击在砧座上。每分钟振动250±15次，振动12分钟。测定量筒内正极活性材料的容积，正极活性材料质量与容积的比值即为正极活性材料的振实密度。
振实密度的计算公式为：ρbt＝m0/V
其中，ρbt——振实密度，g/cm3
m0——正极活性材料的质量，g
V——振实后正极活性材料的体积(量杯的容积)，cm3。
在本申请一些实施方式中，所述正极活性材料在300MPa压力下的压实密度为3.0g/cm3-4.0g/cm3，例如正极活性材料在300MPa压力下的压实密度可以是3.0g/cm3-3.9g/cm3，3.1g/cm3-3.8g/cm3，3.2g/cm3-3.7g/cm3，3.3g/cm3-3.6g/cm3，3.4g/cm3-3.5g/cm3等。
在本申请一些实施方式中，压实密度指的是材料制成极片之后极片的压实密度。压实密度＝面密度/(极片碾压后的厚度-集流体厚度)，具体的，正极活性材料的300MPa压力下的压实密度的测定方法如下：
取辊压后的极片，用面积为s的圆形或者方形裁刀切下一块区域，测量厚度为a，并称重为m1，用丙酮酒精混合液洗去正极材料并吹干，称取剩下铝箔重量m2，并测量铝箔厚度为b。两者重量之差除以圆形或方形的面积s，计算面密度，即面密度＝(m1-m2)/s。面密度除以厚度差，即为压实密度，即压实密度＝(m1-m2)/[s(a-b)]。
具体的，当本申请的正极活性材料的Dv50、比表面积、振实密度和300MPa压力下的压实密度中的至少之一在上述范围时，正极活性材料内的传导距离小、表面副反应少，促进了正极活性材料发挥其克容量，提升了含有其的电池的容量保持率。
本申请第二方面提供了一种制备第一方面所述的正极活性材料的方法，包括：
S100：将Na源、Ni源、Fe源、Mn源、M1源和M2源混合得到前驱体
在本申请中的一些实施例中，将Na源、Ni源、Fe源、Mn源、M1源和M2源按照上述正极活性 材料组成进行混合。
需要说明的是，本申请中的Na源、Ni源、Fe源、Mn源、M1源和M2源是本领域常规材料，本领域技术人员可根据实际进行选择，例如Na源可以包括Na2CO3、NaHCO3、NaOH和Na2O2中的至少一种；Ni源可以包括NiO；Fe源可以包括FeO、Fe2O3和Fe3O4中的至少一种；Mn源可以包括Mn2O3、Mn3O4、MnO、MnO2中的至少一种；M1源可以包括M1的氧化物、含M1的盐和其他化合物中的至少一种；M2源可以包括M2的氧化物、含M2的盐和其他化合物中的至少一种。
需要说明的是，若需要在正极活性材料中掺杂F元素，则Na源、Ni源、Fe源、Mn源、M1源和M2源中至少之一采用其对应含氟盐和其他化合物中的至少一种，例如氟化钠、氟化镍、氟化铁、氟化锰、氟化M1(M1的氟化盐)和氟化M2(M2的氟化盐)。
S200：将所述前驱体进行煅烧
在本申请的一些实施方式中，将上述所得前驱体置于马弗炉于空气气氛中煅烧，然后冷却至室温后，机械粉碎后得到所述正极活性材料，其中煅烧温度可以是600℃-1200℃，例如可以是600℃-1100℃，700℃-1000℃，800℃-900℃等，保温时间为10h-20h，例如可以是10h-19h，11h-18h，12h-17h，13h-16h，14h-15h等。
此外，可根据需要，在对前驱体煅烧之前，预先对前驱体进行预煅烧并保温，预煅烧温度可以是600℃-900℃，例如可以是600℃-850℃，650℃-800℃，600℃-750℃，550℃-700℃，500℃-650℃，550℃-600℃等，保温时间为10h-20h，例如可以是10h-19h，11h-18h，12h-17h，13h-16h，14h-15h等。
由此，采用固相法可以制备上述具有优异的空气稳定性和循环稳定性的正极活性材料，提高电池的容量保持率。
本申请第三方面提供了另一种制备第一方面所述的正极活性材料的方法，包括：
Sa：将Ni源、Fe源、Mn源、M1源和M2源与水混合得到混合溶液
在本申请中的一些实施例中，将Ni源、Fe源、Mn源、M1源和M2源按照上述正极活性材料组成与水混合得到混合溶液。
需要说明的是，本申请中的Ni源、Fe源、Mn源、M1源和M2源是本领域常规材料，本领域技术人员可根据实际进行选择，例如Ni源可以包括氯化镍、硫酸镍、硝酸镍、草酸镍中的至少一种；Fe源可以包括氯化铁、硫酸铁、硝酸铁、草酸铁中的至少一种；Mn源可以包括氯化锰、硫酸锰、硝酸锰、草酸锰中的至少一种；M1源可以包括M1的氯化物、硫酸盐、硝酸盐、草酸盐中的至少一种；M2源可以包括M2的氯化物、硫酸盐、硝酸盐、草酸盐和其他化合物中的至少一种。
Sb：将所述溶液与沉淀剂反应得到前驱体
在本申请的一些实施方式中，将步骤Sa所得的溶液与含有沉淀剂的溶液进行反应，得到前驱体，其中的含有沉淀剂的溶液包括氨水、碳酸和草酸中的至少之一。
Sc：将前驱体与Na源混合后进行煅烧
在本申请的一些实施方式中，将所得前驱体与Na源按照上述正极活性材料组成混合球磨或机械搅拌混合均匀后，置于马弗炉中煅烧，然后冷却至室温，机械粉碎后得到所述正极活性材料，其中煅烧温度为600℃-1200℃，例如可以是700℃-1100℃，800℃-1000℃，900℃-950℃等，煅烧气氛可以为空气或氧气气氛，保温时间为10h-20h，例如可以是10h-19h，11h-18h，12h-17h，13h-16h，14h-15h等。
需要说明的是，可根据需要，在对前驱体和Na源混合煅烧之前，预先对前驱体Na源混合后进行预煅烧并保温，预煅烧温度可以是600℃-900℃，例如可以是600℃-850℃，650℃-800℃，600℃-750℃，550℃-700℃，500℃-650℃，550℃-600℃等，保温时间可以是10h-20h，例如可以是10h-19h，11h-18h，12h-17h，13h-16h，14h-15h等。Na源可以包括Na2CO3、NaHCO3、NaOH、Na2O2中的至少一种。
需要说明的是，若需要在正极活性材料中掺杂F元素，则Na源、Ni源、Fe源、Mn源、M1源和M2源中至少之一采用其对应含氟盐和其他化合物中的至少一种，例如氟化钠、氟化镍、氟化铁、氟化锰、氟化M1(M1的氟化盐)和氟化M2(M2的氟化盐)。
由此，采用共沉淀法可以制备上述具有优异的空气稳定性和循环稳定性的正极活性材料，提高电池的容量保持率。
本申请第四方面提供了一种正极极片，其包括本申请第一方面所述的正极活性材料、第二方面所述的方法制备的正极活性材料或第三方面所述的方法制备的正极活性材料。
所述正极极片通常包括正极集流体及设置在正极集流体上的正极活性物质层，所述正极活性物质层包括正极活性材料。
所述正极集流体可以采用常规金属箔片或复合集流体(可以将金属材料设置在高分子基材上形成复合集流体)。作为示例，正极集流体可以包括铜箔、铝箔、镍箔、不锈钢箔、不锈钢网及涂炭铝箔中的至少一种。
所述正极活性材料包括本申请第一方面所述的正极活性材料、第二方面所述的方法制备的正极活性材料或第三方面所述的方法制备的正极活性材料。
正极活性物质层还可选的包括导电剂和粘结剂，导电剂用于改善正极活性物质层的导电性，粘结剂用于将正极活性材料及粘结剂牢固地粘结于正极集流体上。本申请对导电剂和粘结剂的种类不做具体限定，可以根据实际需求进行选择。
作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种；粘结剂可以包括丁苯橡胶(SBR)、水性丙烯酸树脂(water-basedacrylic resin)、羧甲基纤维素(CMC)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、乙烯-醋酸乙烯酯共聚物(EVA)及聚乙烯醇(PVA)中的至少一种。
这些材料均可以通过商业途径获得。
本申请第五方面提供了一种电池，其包括本申请第四方面的所述的正极极片。由此，该电池具有优异的容量保持率。
电池，是指在放电后可通过充电的方式使活性材料激活而继续使用的电池。
可以理解的是，本申请提出的电池是钠离子电池。
通常情况下，电池包括正极极片、负极极片、隔离膜及电解液。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。隔离膜设置在正极极片和负极极片之间，起到隔离的作用。电解质在正极极片和负极极片之间起到传导离子的作用。
[负极极片]
在电池中，所述负极极片通常包括负极集流体及设置在负极集流体上的负极活性材料层，所述负极活性材料层包括负极活性材料。
所述负极集流体可以采用常规金属箔片或复合集流体(例如可以将金属材料设置在高分子基材上形成复合集流体)。作为示例，负极集流体可以采用铜箔。
所述负极活性材料的具体种类不做限制，可以采用本领域已知的能够用于钠离子电池负极的活性材料，本领域技术人员可以根据实际需求进行选择。作为示例，所述负极活性材料可以包括但不限于钠金属、碳材料、合金材料、过渡金属氧化物和/或硫化物、磷基材料、钛酸盐材料中的至少一种。具体地，所述碳材料可包括硬碳、软碳、无定形碳、纳米结构碳材料中的至少一种；所述合金材料可包括Si、Ge、Sn、Pb、Sb中的至少一种形成的合金材料；所述过渡金属氧化物和硫化物的通式为MxNy，其中M包括Fe、Co、Ni、Cu、Mn、Sn、Mo、Sb、V的至少一种，N包括O或S；所述磷基材料可包括红磷、白磷、黑磷中的至少一种；所述钛酸盐材料可包括Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3中的至少一种。这些材料均可以通过商业途径获得。
所述负极活性材料层通常还可选地包括粘结剂和导电剂，导电剂用于提高负极活性物质层的导电性，粘结剂用于将负极活性材料及粘结剂牢固地粘结于负极集流体上。本申请对导电剂和粘结剂的种类不做具体限定，可以根据实际需求进行选择。
作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中至少一种。
作为示例，粘结剂可以包括丁苯橡胶(SBR)、苯乙烯-丁二烯橡胶(SBCs)、水性丙烯酸树脂(water-based acrylic resin)及羧甲基纤维素(CMC)中的至少一种。
负极活性材料层还可选的包括增稠剂，如羧甲基纤维素(CMC)。但本申请并不限于此，本申请还可以使用其它可被用作钠离子电池负极极片增稠剂的材料。
[电解液]
所述电解液可以包括电解质盐和溶剂。
作为示例，所述电解质钠盐可以包括六氟磷酸钠、二氟草酸硼酸钠、四氟硼酸钠、双草酸硼酸钠、高氯酸钠、六氟砷酸钠、双(氟磺酰)亚胺钠、三氟甲基磺酸钠和双(三氟甲基磺酰)亚胺钠中的至少之一。
作为示例，所述溶剂可包括碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、 碳酸亚丁酯(BC)、氟代碳酸亚乙酯(FEC)、甲酸甲酯(MF)、乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸甲酯(MP)、丙酸乙酯(EP)、丙酸丙酯(PP)、丁酸甲酯(MB)、丁酸乙酯(EB)、1，4-丁内酯(GBL)、环丁砜(SF)、二甲砜(MSM)、甲乙砜(EMS)及二乙砜(ESE)中的至少一种。
在一些实施方式中，电解液中还包括添加剂。例如添加剂可以包括负极成膜添加剂，也可以包括正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温性能的添加剂、改善电池低温性能的添加剂。
[隔离膜]
作为上述的隔离膜，本申请并没有特别的限制，可以根据实际需求选用任意公知的具有电化学稳定性和力学稳定性的多孔结构隔离膜，例如可以包括包含玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种的单层或多层薄膜。
本申请实施例对电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。如图1是作为一个示例的方形结构的电池1。
在一些实施方式中，电池可包括外包装。该外包装用于封装正极极片、负极极片和电解质。
在一些实施方式中，外包装可包括壳体和盖板。其中，壳体可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体具有与容纳腔连通的开口，盖板能够盖设于所述开口，以封闭所述容纳腔。
正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件。电极组件封装于所述容纳腔。电池所含电极组件的数量可以包括一个或几个，可根据需求来调节。
在一些实施方式中，电池的外包装可以包括硬壳，例如硬塑料壳、铝壳、钢壳。
电池的外包装也可以包括软包，例如袋式软包。软包的材质可以是塑料，如可包括聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)、聚丁二酸丁二醇酯(PBS)中的至少一种。
在一些实施方式中，电池可以组装成电池模块，电池模块所含电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
图2是作为一个示例的电池模块2。参照图2，在电池模块2中，多个电池1可以是沿电池模块2的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个电池1进行固定。
电池模块2还可以包括具有容纳空间的外壳，多个电池1容纳于该容纳空间。在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
图3和4是作为一个示例的电池包3。参照图3和4，在电池包3中可以包括电池箱和设置于电池箱中的多个电池模块2。电池箱包括上箱体4和下箱体5，上箱体4能够盖设于下箱体5，并形成用于容纳电池模块2的封闭空间。多个电池模块2可以按照任意的方式排布于电池箱中。
本申请第六方面提供了一种用电设备，其包括第五方面所述的电池。具体的，所述电池可以作为所述用电设备的电源，也可以作为所述用电设备的能量存储单元。所述用电设备可以包括但不限于移动设备(例如手机、笔记本电脑)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车)、电气列车、船舶及卫星、储能系统。
图5是作为一个示例的用电设备。该用电设备包括纯电动车、混合动力电动车、或插电式混合动力电动车。
作为另一个示例的用电设备可以包括手机、平板电脑、笔记本电脑。该用电设备通常要求轻薄化，可以采用电池作为电源。
为了使本申请实施例所解决的技术问题、技术方案及有益效果更加清楚，以下将结合实施例和附图进行进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本申请及其应用的任何限制。基于本申请中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例都属于本申请保护的范围。
实施例1
【NaNi0.2Fe0.2Mn0.5La0.02Cu0.08O2制备】
原料按分子式化学计量比，将23.666g的Na2CO3、6.672g的NiO、7.131g的Fe2O3、17.627g的Mn2O3、1.455g的La2O3和2.841g的CuO原料(Na，Ni，Fe，Mn，La和Cu的摩尔比为1：0.2：0.2：0.5：0.02：0.08)混合在行星式球磨机的玛瑙球磨罐中，采用600r/min的转速将原料研磨，然后在马弗炉中按5℃/min的升温速率升高温度到950℃，保温煅烧15h后自然降温到室温，得到黑色的正极活性材料NaNi0.2Fe0.2Mn0.5La0.02Cu0.08O2。
【正极极片的制备】
将上述制备的NaNi0.2Fe0.2Mn0.5La0.02Cu0.08O2、导电剂碳黑、粘结剂聚偏二氟乙烯(PVDF)、N-甲基吡咯烷酮(NMP)按重量比为60：5：5：30搅拌混合均匀，得到正极浆料；将正极浆料均匀涂覆于正极铝箔集流体上，经过烘干、冷压、分切，得到正极极片。
【负极极片的制备】
负极极片采用金属钠片。
【电解液的制备】
在氩气气氛手套箱中(H2O<0.1ppm，O2<0.1ppm)，将有机溶剂碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)按照体积比3/7混合均匀得到混合溶剂，然后将NaPF6溶解于混合溶剂中，搅拌均匀，得到钠盐浓度1mol/L的电解液。
【隔离膜】
以玻璃纤维作为隔离膜。
将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极极片之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装中，将上述制备好的电解液注入到干燥后的二次电池中，经过真空封装、静置、化成、整形工序，获得二次电池。
实施例2-24和对比例1-4的含有正极活性材料的二次电池，除参数不同外(参见表1)，其余与实施例1相同。
本申请实施例1-24和对比例1-4的电池中正极活性材料的组成如表1所示。
表1

对实施例1-24和对比例1-4中正极活性材料的Dv50、比表面积、振实密度、300MPa压力下的压实密度、浸泡液的pH值、相态、空间群和层间距以及所得钠离子电池的容量和容量保持率进行表征，表征结果如表2所示。
性能测试：
1、正极活性材料相态、空间群和层间距测试：对正极活性材料做XRD图，根据XRD图谱中特征峰的位置确定正极活性材料的相态和空间群，根据X射线衍射的(003)峰或(002)峰的位置，并根据对应的峰及公式d＝λ/(2sinθ)计算得到正极活性材料的层间距d，公式d＝λ/(2sinθ)中，射线波长扫描2θ角在40.5°至42.5°范围内的特征峰表示正极活性材料为O3相，空间群包括扫描2θ角在48°至50°范围内的特征峰表示正极活性材料为P2相，空间群包括P63/mmc。
2、正极活性材料的Dv50测定：参照GB/T 19077-2016，使用Malvern Master Size 3000激光粒度分析仪进行测定。
3、振实密度测定：将称量好的正极活性材料装入振实装置量筒，将量筒固定在支座上。转动凸轮，定向杆带动支座上、下滑动，并撞击在砧座上。每分钟振动250±15次，振动12分钟。测定量筒内正极活性材料的容积，正极活性材料质量与容积的比值即为正极活性材料的振实密度。
振实密度的计算公式为：ρbt＝m0/V
其中，ρbt——振实密度，g/cm3
m0——正极活性材料的质量，g
V——振实后正极活性材料的体积(量杯的容积)，cm3。
4、正极活性材料的300MPa压力下的压实密度：取辊压后的极片，用面积为s的圆形或者方形裁刀切下一块区域，测量厚度为a，并称重为m1，用丙酮酒精混合液洗去正极材料并吹干，称取剩下铝箔重量m2，并测量铝箔厚度为b。两者重量之差除以圆形或方形的面积s，计算面密度，即面密度＝(m1-m2)/s。面密度除以厚度差，即为压实密度，即压实密度＝(m1-m2)/[s(a-b)]。
5、正极活性材料的浸泡液的pH值测定：将正极活性材料分散到纯水中浸泡，过滤得到浸泡液，量取浸泡液用标准盐酸溶液滴定。
6、正极极片的容量测试：制作正极极片，制作负极极片，冲模、称重，按照正负极材料种类选择正负极片极片的质量进行对应配对，然后放置于手套箱中2h；手套箱扣电组装，将制作完成的扣式电池夹持在电化学测试柜上，根据测试倍率(0.2C、1C、3C、5C)计算充放电电流，电流＝倍率×理论克容 量×(M2-M1)×ω％式中：理论克容量——根据正极材料的理论克容量决定；
M2——极片的实称重量；
M1——集流体的平均重量；
ω％——活性物质实际质量分数
7、电池容量保持率测试：
以实施例1为例，在25℃下，将二次电池以0.1C倍率恒流充电至充电截止电压4.2V，之后再以0.1C放电至1.5V，静置5min，再以0.5C倍率恒流放电至放电截止电压2.8V，静置5min，记录此时的电池放电容量C0。按照此方法对电池进行500次循环充放电，记录500次循环后的电池放电容量记为C1。
二次电池的循环容量保持率＝C1/C0×100％。
实施例2-24和对比例1-4的二次电池的容量保持率的测试过程同上。
实施例1、对比例1和对比例2的正极活性材料的XRD图如图6和图7所示，对比例1与实施例1相比，正极活性材料中稀土元素M1与Mn的比例d/c为0.004，小于0.005，正极活性材料的10-20之间的峰不明显，而在30-40之间的杂峰更明显，可知稀土元素过少，不利于提高正极活性材料的空气稳定性和循环稳定性；对比例2与实施例1相比，正极活性材料中稀土元素M1与Mn的比例d/c为0.06，大于0.05，正极活性材料有明显的杂峰，可知稀土元素过多，稀土元素与Mn之间固溶度不足而导致稀土元素在正极活性材料表面团聚而生成杂相。
图8为实施例1制备的钠离子电池在首圈0.1C下的充放电曲线，可知电池的工作电压范围为1.5V-4.2V。
实施例1和对比例4的容量保持率对比图如图9所示，可知，本申请实施例1的容量保持率明显优于对比例4。
表2

由表2可以看出，本申请实施例中，以NiFeMn为主体材料且掺杂稀土元素M1和掺杂元素M2并控制稀土元素M1和Mn的比例，可以提高正极活性材料的空气稳定性和循环稳定性，从而提升含有其的电池的容量保持率。相比于实施例，对比例1和2中d/c的值不在本申请实施例的范围内，对比例3和4中Mn的含量c的值不在本申请实施例的范围内，含有其的电池的容量保持率和容量均明显降低。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，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申请各实施例技术方案的范围，其均应涵盖在本申请的权利要求和说明书的范围当中。尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (15)

  1. 一种正极活性材料，其中，所述正极活性材料包括：
    NaxNiaFebMncM1dM2eO2+δ-fFf，
    其中，M1包括稀土元素，M2包括第ⅠA族元素、第ⅡA族元素、第ⅢA族元素、第ⅣA族元素、第ⅤA族元素、第ⅥA族元素和过渡元素中的至少一种，0.6≤x≤1.2，0＜a≤0.5，0＜b≤0.4，0.3≤c≤0.75，0.001≤d≤0.05，0≤e≤0.3，-0.1≤δ≤0.1，0≤f≤0.1，0.005≤d/c≤0.05，a+b+c+d+e＝1。
  2. 根据权利要求1所述的正极活性材料，其中，所述稀土元素包括La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的至少一种。
  3. 根据权利要求1或2所述的正极活性材料，其中，所述M2包括B、Mg、Al、Si、K、Ca、Ga、Ge、Se、Rb、Sr、In、Sn、Sb、Te、Sc、Ti、V、Cr、Co、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt和Au的至少一种。
  4. 根据权利要求1-3中任一项所述的正极活性材料，其中，0.01≤d/c≤0.03。
  5. 根据权利要求1-4中任一项所述的正极活性材料，其中，所述正极活性材料满足以下条件中的至少之一：
    0.1≤a≤0.4，可选为0.15≤a≤0.3；
    0.1≤b≤0.35，可选为0.15≤b≤0.35；
    0.35≤c≤0.6，可选为0.35≤c≤0.5。
  6. 根据权利要求1-5中任一项所述的正极活性材料，其中，1.75≤(a+b+c)/b≤9.5，可选地，2≤(a+b+c)/b≤9.5，更可选地，2≤(a+b+c)/b≤6.3。
  7. 根据权利要求1-6中任一项所述的正极活性材料，其中，0.8＜x≤1.0，所述正极活性材料的相态包括O3相，空间群包括层间距为0.53nm-0.55nm。
  8. 根据权利要求1-6中任一项所述的正极活性材料，其中，0.6≤x≤0.8，所述正极活性材料的相态包括P2相，空间群包括P63/mmc，层间距为0.54nm-0.57nm。
  9. 根据权利要求1-8中任一项所述的正极活性材料，其中，所述正极活性材料的浸泡液的pH值小于或等于13，可选地，所述正极活性材料的浸泡液的pH值小于或等于12.7，更可选地，所述正极活性材料的浸泡液的pH值为11.0≤pH≤12.7。
  10. 根据权利要求1-9中任一项所述的正极活性材料，其中，所述正极活性材料满足以下条件中的至少之一：
    所述正极活性材料的Dv50为3μm-30μm，可选为5μm-15μm；
    所述正极活性材料的比表面积为0.1m2/g-5m2/g，可选为0.3m2/g-3m2/g；
    所述正极活性材料的振实密度为1g/cm3-3g/cm3，可选为1.5g/cm3-2.5g/cm3；
    所述正极活性材料在300MPa压力下的压实密度为3.0g/cm3-4.0g/cm3。
  11. 一种制备权利要求1-10中任一项所述的正极活性材料的方法，其中，包括：
    将Na源、Ni源、Fe源、Mn源、M1源和M2源混合得到前驱体；
    将所述前驱体进行煅烧，得到正极活性材料。
  12. 一种制备权利要求1-10中任一项所述的正极活性材料的方法，其中，包括：
    将Ni源、Fe源、Mn源、M1源和M2源与水混合得到混合溶液；
    将所述溶液与沉淀剂反应得到前驱体；
    将前驱体与Na源混合后进行煅烧，得到正极活性材料。
  13. 一种正极极片，其中，所述正极极片包括权利要求1-10中任一项所述的正极活性材料或者采用权利要求11或12所述的方法制备的正极活性材料。
  14. 一种电池，其中，所述电池包括权利要求13所述的正极极片。
  15. 一种用电设备，其中，包括权利要求14所述的电池。
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