WO2025007458A1 - 正极活性材料及其制备方法、正极极片、电池和用电装置 - Google Patents

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

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WO2025007458A1
WO2025007458A1 PCT/CN2023/127831 CN2023127831W WO2025007458A1 WO 2025007458 A1 WO2025007458 A1 WO 2025007458A1 CN 2023127831 W CN2023127831 W CN 2023127831W WO 2025007458 A1 WO2025007458 A1 WO 2025007458A1
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Prior art keywords
positive electrode
manganese oxide
sodium
phase
active material
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PCT/CN2023/127831
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English (en)
French (fr)
Inventor
吴凯
梁子彬
王宇豪
林文光
李强
张欣欣
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP23944179.3A priority Critical patent/EP4742317A1/en
Priority to JP2025558546A priority patent/JP2026517100A/ja
Priority to KR1020267003849A priority patent/KR102989666B1/ko
Publication of WO2025007458A1 publication Critical patent/WO2025007458A1/zh
Priority to US19/440,646 priority patent/US20260155365A1/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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)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
    • C01G53/42—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
    • 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
    • C01G53/42—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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    • 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
    • C01G53/51—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 containing sodium
    • 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
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/78—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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the first phase is a P2 phase, and the space group is P63/mmc; the second phase is an O3 phase, and the space group is R3m.
  • the synergistic effect between the P2 phase and the O3 phase can further improve the cycle stability and specific capacity of the positive electrode active material.
  • the positive electrode active material can be obtained by a two-step calcination process, and the interlayer spacing d 1 of the first transition metal layers adjacent to each other in the first phase in a direction perpendicular to the (001) crystal plane and the interlayer spacing d 2 of the second transition metal layers adjacent to each other in the second phase in a direction perpendicular to the (001) crystal plane are precisely controlled.
  • the calcination treatment satisfies at least one of the following conditions: the calcination treatment temperature is 800° C.-900° C.; the calcination treatment time is 0.5 h-20 h.
  • the calcination treatment temperature is 800° C.-900° C.
  • the calcination treatment time is 0.5 h-20 h.
  • the first calcination treatment satisfies at least one of the following conditions: the temperature of the first calcination treatment is 700° C.-900° C.; the time of the first calcination treatment is 10 h-20 h.
  • a second sodium manganese oxide with a desired interlayer spacing can be obtained.
  • the second calcination treatment satisfies at least one of the following conditions: the temperature of the second calcination treatment is 800° C.-1100° C.; the time of the second calcination treatment is 10 h-20 h.
  • the present application proposes a battery, comprising the aforementioned positive electrode sheet. Therefore, the battery has all the features and advantages of the aforementioned positive electrode sheet, which will not be described in detail here.
  • the present application proposes an electrical device, comprising the aforementioned battery. Therefore, the electrical device has all the features and advantages of the aforementioned battery, which will not be described in detail here.
  • FIG1 is a schematic diagram of the interlayer spacing of sodium manganese oxide
  • FIG2 shows a schematic diagram of a battery according to an embodiment of the present application
  • FIG3 is an exploded view of the battery of an embodiment of the present application shown in FIG2 ;
  • FIG4 shows a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG5 shows a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG6 is an exploded view of the battery pack of one embodiment of the present application shown in FIG5 ;
  • FIG7 shows a schematic diagram of an electrical device using a battery as a power source according to an embodiment of the present application
  • FIG8 shows the XRD diffraction spectrum of the positive electrode active material in Example 1 of the present application.
  • FIG. 9 shows the XRD diffraction spectrum of the positive electrode active material in Comparative Example 1 of the present application.
  • a and/or B may include the case of A alone, the case of B alone, or any of the cases of A and B, where A and B are only used for examples and may be any technical feature connected by “and/or" in the present application.
  • the sodium manganese oxide with a layered structure will continuously undergo sodium ion deintercalation during the charge and discharge cycle.
  • the layered structure of the sodium manganese oxide will shrink and expand to complete the sodium ion deintercalation.
  • the stress on the layered structure of the sodium manganese oxide during the shrinkage and expansion process is too large, the layered structure of the sodium manganese oxide will be destroyed by the excessive stress, resulting in defects and cracks inside the sodium manganese oxide particles, which in turn leads to poor cycle stability of the positive electrode active material.
  • the present application proposes a sodium manganese oxide positive electrode active material with a mixed phase, in which the interlayer spacing d 1 of adjacent first transition metal layers in the first phase in the positive electrode active material in a direction perpendicular to the (001) crystal plane, and the interlayer spacing d 2 of adjacent second transition metal layers in the second phase in a direction perpendicular to the (001) crystal plane, the difference between d 1 and d 2 is between 0.01nm and 0.02nm, so that in the process of contraction and expansion of the sodium manganese oxide layered structure, it will play an "interlocking" role, so that the sodium manganese oxide layered structure is subjected to less stress during the process of sodium insertion and deinsertion, thereby reducing the strain of the crystal structure, reducing the defects and cracks caused by excessive strain in the crystal structure, and improving the stability of the positive electrode active material during the charge and discharge cycle.
  • the aforementioned interlayer spacing refers to the distance between two adjacent transition metal layers in the direction perpendicular to the (001) crystal plane in the sodium manganese layered oxide.
  • a battery typically includes a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator.
  • active ions such as active sodium ions
  • the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the separator is set between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer at least located on one side of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.
  • the battery disclosed in the embodiments of the present application can be used in an electrical device that uses the battery as a power source, or a power supply system that uses the battery disclosed in the present application to form the electrical device, or various energy storage systems that use the battery as an energy storage element.
  • Electrical devices may include mobile phones, tablets, laptops, electric toys, electric tools, battery cars, electric cars, ships, spacecraft, etc.
  • electric toys may include fixed or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc.
  • spacecraft may include airplanes, rockets, space shuttles, and spacecrafts, etc.
  • the present application proposes a positive electrode active material, including sodium manganese oxide, the sodium manganese oxide including a first phase and a second phase, the first phase including a first sodium ion layer and a first transition metal layer alternating in sequence, and the second phase including a second sodium ion layer and a second transition metal layer alternating in sequence; the interlayer spacing of adjacent first transition metal layers in the first phase in a direction perpendicular to the (001) crystal plane is d 1 , and the interlayer spacing of adjacent second transition metal layers in the second phase in a direction perpendicular to the (001) crystal plane is d 2 , d 1 -d 2 is 0.01nm-0.02nm, because the interlayer spacing of the first phase is slightly larger than the interlayer spacing of the second phase, the strain generated in the first phase and the second phase during the sodium insertion and extraction process can be small, reducing the occurrence of defects and cracks in the crystal structure, thereby improving the cycle stability of the positive electrode active
  • d 1 -d 2 when d 1 -d 2 is less than 0.01 nm, the "interlocking" effect between the first phase and the second phase is not obvious, and the cycle stability of the positive electrode active material cannot be improved; when d 1 -d 2 is greater than 0.02 nm, the interlayer spacing between the first phase and the second phase is too large, and the synergistic effect between the two phases during the charge and discharge cycle is poor, which is not conducive to the insertion and extraction of sodium ions.
  • d 1 -d 2 may be 0.01 nm, 0.011 nm, 0.012 nm, 0.013 nm, 0.014 nm, 0.015 nm, 0.016 nm, 0.017 nm, 0.018 nm, 0.019 nm, or 0.02 nm.
  • the sodium manganese oxide may include a doping element Q, thereby further improving the structural stability and specific capacity of the positive electrode active material.
  • the doping element Q may include a second doping element Q2, the second doping element partially replaces the manganese element in the sodium manganese oxide, and the second doping element includes at least one of Fe, Co, Ni, Cu, Zn, Ga, Li, B, Mg, Al, Si, Ti, Y, Zr, Nb, Mo, In, Sn, Sb, La, Ce, Ta, W, and Bi.
  • the specific capacity, average discharge voltage, structural stability, etc. of the positive electrode active material can be improved.
  • the positive electrode active material after the positive electrode active material has been subjected to sodium supplementation, chemical formation and other processes, and has been used for a long time, the positive electrode active material
  • the sodium content may exceed the standard value due to the sodium supplementation process, or it may be lower than the standard value after formation and long-term circulation; the oxygen content in the positive electrode active material may also be lower than the standard value due to the release of lattice oxygen in the later stage of the cycle.
  • S 1 diffraction peak intensity of the first transition metal layer/first sodium ion layer in the first phase to X-rays within 2 ⁇ of 13°-16.2°
  • S 2 the diffraction peak intensity of the second transition metal layer/second sodium ion layer in the second phase to X-ray
  • the phase with a larger interlayer distance in the positive electrode active material is beneficial to the high-voltage phase transition of the positive electrode active material, thereby effectively increasing the average discharge voltage of the positive electrode active material and further increasing the energy density of the positive electrode active material.
  • the Ni in the positive electrode active material can provide charge compensation during the charge and discharge process, thereby increasing the specific capacity of the positive electrode active material.
  • the Ni in the transition metal layer of the sodium manganese oxide with a large interlayer spacing easily migrates to the sodium ion layer, thereby destroying the layered structure of the sodium manganese oxide and reducing the cycle stability.
  • the positive electrode active material has a higher specific capacity, a higher average discharge voltage, and better cycle stability.
  • the average discharge voltage of the positive electrode active material and the structural stability during the cyclic charge and discharge process can be further improved.
  • the structural stability and specific capacity of the positive electrode active material can be
  • Ni and Fe located in the first transition metal layer in the first phase with a larger interlayer spacing easily migrate to the first sodium ion layer, thereby causing the layered structure of the sodium manganese oxide to be destroyed and the cycle stability to decrease.
  • the specific capacity of the positive electrode active material can be increased by controlling the content of Fe and Ni to be relatively high, that is, 0.1 ⁇ (d1 ⁇ e1)/(y1 2 ) ⁇ 1.
  • the diffraction peak intensity of the first transition metal layer/first sodium ion layer in the first phase for X-rays within 2 ⁇ of 13°-16.2° is S 1
  • the diffraction peak intensity of the second transition metal layer/second sodium ion layer in the second phase for X-rays within 2 ⁇ of 16.2°-17° is S 2
  • S 1 and S 2 satisfy 0.01 ⁇ S 1 /(S 1 +S 2 ) ⁇ 0.5.
  • the positive electrode active material can have a higher specific capacity while having a higher cycle stability.
  • 0.05 ⁇ S 1 /(S 1 +S 2 ) ⁇ 0.5 is optionally, the structural stability and specific capacity of the positive electrode active material can be further improved.
  • the diffraction peak intensity of X-rays in a specific 2 ⁇ range of the transition metal layer/sodium ion layer in the positive electrode active material refers to:
  • the crystal structure formed by the adjacent transition metal layers and sodium ion layers in the active material has a strong diffraction peak for X-rays within a specific 2 ⁇ range.
  • the diffraction peak intensity S1 of the first transition metal layer/first sodium ion layer in the first phase to X-rays and the diffraction peak intensity S2 of the second transition metal layer/second sodium ion layer in the second phase to X-rays can be obtained by testing as follows: XRD test is performed on the positive electrode active material, using CuK ⁇ rays as the radiation source, and the ray wavelength is The scanning 2 ⁇ angle range is 5°-60°, and the scanning rate is 4°/min for testing, wherein the 2 ⁇ angle peak is within 15°-17°.
  • the respective diffraction peak intensities can be obtained after full spectrum fitting Rietveld peak separation.
  • the interlayer spacing of adjacent transition metal layers in the corresponding first phase and second phase in the direction perpendicular to the (001) crystal plane can be obtained.
  • the synergistic effect of the first phase and the second phase during the cycle process can be utilized to improve the structural stability of the positive electrode active material during the cycle process.
  • the elemental composition of the positive electrode active material can be tested by inductively coupled plasma emission spectrometry.
  • the instrument standard refers to EPA6010D-2014 "Inductively coupled plasma atomic emission spectrometry".
  • the sample to be tested is treated by chemical methods and digested into a solution, it is atomized into a plasma and excited to produce characteristic spectral lines of the elements.
  • the element content is qualitatively and quantitatively analyzed based on the wavelength and intensity of the spectral lines (which are proportional to the concentration).
  • the composition of each of the two phases in the positive electrode active material can be obtained by performing elemental analysis on the particles of different phases after ion polishing the cross section of the sample to be tested.
  • the first phase is the P2 phase, and the space group is P63/mmc; the second phase is the O3 phase, and the space group is R3m. Since the oxygen layer arrangement between the P2 phase and the O3 phase is inconsistent, it helps to improve the "interlocking" effect between the first phase and the second phase, thereby further improving the cycle stability of the positive electrode active material.
  • the space group of the positive electrode active material can be confirmed.
  • the pH of a deionized water solution of a positive electrode active material with a mass concentration of 2 g/18 mL may be 7-13; alternatively, the pH is 11-12.5.
  • the pH value of the positive electrode active material may be 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, or 13.
  • the positive electrode active material may be weakly alkaline, so that it is easy to subsequently form a positive electrode slurry suitable for coating, and the pH of the positive electrode active material is 7-13.
  • the pH of the positive electrode active material may meet 11-13, and further, the pH of the positive electrode active material may meet 11-12.5, so that the generation of gelation during the slurry adjustment process can be reduced and the coating stability of the positive electrode slurry can be improved.
  • the pH of the positive electrode active material of the present application is measured by the following method: after determining the elemental composition of the positive electrode active material by ICP, 2 g of the positive electrode active material is added to 18 mL of deionized water, stirred at room temperature (25°C) until completely dissolved, and allowed to stand for 30 minutes. The pH of the obtained supernatant is tested, and the measured pH result is the pH of the positive electrode active material.
  • the present application proposes a method for preparing the aforementioned positive electrode active material, comprising: providing a precursor; calcining the precursor to obtain the positive electrode active material, wherein the positive electrode active material comprises sodium manganese oxide, the sodium manganese oxide comprises a first phase and a second phase, the first phase comprises a first sodium ion layer and a first transition metal layer that are alternately arranged in sequence; the second phase comprises a second sodium ion layer and a second transition metal layer that are alternately arranged in sequence; the interlayer spacing of adjacent first transition metal layers in the first phase in a direction perpendicular to the (001) crystal plane is d 1 , and the interlayer spacing of adjacent second transition metal layers in the second phase in a direction perpendicular to the (001) crystal plane is d 2 , and d 1 -d 2 is 0.01nm-0.02nm.
  • the aforementioned positive electrode active material can be prepared by a relatively simple method.
  • the aforementioned positive electrode active material can be obtained by a two-step calcination process, and the interlayer spacing of adjacent first transition metal layers in the first phase in a direction perpendicular to the (001) crystal plane and the interlayer spacing of adjacent second transition metal layers in the second phase in a direction perpendicular to the (001) crystal plane can be precisely controlled.
  • the calcination treatment satisfies at least one of the following conditions: the temperature of the calcination treatment may be 800° C.-900° C.; the time of the calcination treatment may be 0.5 h-20 h.
  • the temperature for calcining the mixture of the first sodium manganese oxide and the second sodium manganese oxide can be 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C or 900°C.
  • the interlayer spacing d1 of adjacent first transition metal layers in the first phase in the positive electrode active material in a direction perpendicular to the (001) crystal plane and the interlayer spacing d2 of adjacent second transition metal layers in the second phase in a direction perpendicular to the (001) crystal plane can be more accurately controlled, so that the difference between d1 and d2 is within the aforementioned range, so that the first phase and the second phase will play an "interlocking" role during the contraction and expansion of the sodium manganese oxide layered structure, so that the stress on the sodium manganese oxide layered structure during the sodium insertion and deinsertion process is relatively small, thereby reducing the strain of the crystal structure, reducing the defects and cracks caused by excessive strain in the crystal structure, and improving the stability of the positive electrode active material during the charge and discharge cycle.
  • the calcination time for the mixture of the first sodium manganese oxide and the second sodium manganese oxide can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.
  • the first sodium manganese oxide with a desired interlayer spacing can be obtained.
  • the first calcination treatment satisfies at least one of the following conditions: the temperature of the first calcination treatment may be 700° C.-900° C.; the time of the first calcination treatment may be 10 h-20 h.
  • the temperature of the first calcination treatment when synthesizing the first sodium manganese oxide can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C or 900°C.
  • the time for the first calcination treatment when synthesizing the first sodium manganese oxide can be 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16h, 17h, 18h, 19h or 20h.
  • a first sodium manganese oxide having an interlayer spacing of 0.550nm-0.565nm between adjacent transition metal layers in a direction perpendicular to the (001) crystal plane can be obtained.
  • the second calcination treatment satisfies at least one of the following conditions: the temperature of the second calcination treatment is 800° C.-1100° C.; the time of the second calcination treatment is 10 h-20 h.
  • the temperature of the second calcination treatment when synthesizing the second sodium manganese oxide can be 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C, 900°C, 910°C, 920°C, 930°C, 940°C, 950°C, 960°C, 970°C, 980°C, 990°C, 1000°C, 1010°C, 1020°C, 1030°C, 1040°C, 1050°C, 1060°C, 1070°C, 1080°C, 1090°C or 1100°C.
  • the time for the second calcination treatment when synthesizing the second sodium manganese oxide can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h or 20 h.
  • a second sodium manganese oxide having an interlayer spacing of 0.530 nm-0.545 nm between adjacent transition metal layers in a direction perpendicular to the (001) crystal plane can be obtained.
  • the sodium source may include at least one of Na 2 CO 3 , NaHCO 3 , NaOH, and Na 2 O 2 .
  • the manganese oxide may include at least one of Mn 2 O 3 , Mn 3 O 4 , MnO, and MnO 2 .
  • the present application proposes a positive electrode plate, comprising the aforementioned positive electrode active material, and/or the positive electrode active material prepared by the aforementioned method.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on at least one side of the positive electrode current collector, wherein the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil is, for example, an aluminum foil.
  • the composite current collector may include a polymer base layer and a metal layer formed on at least one side of the polymer base layer, wherein the material of the metal layer includes, but is not limited to, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.; the polymer material of the polymer base layer may be polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material is a positive electrode active substance in the positive electrode active material layer.
  • the positive electrode active material layer may also optionally include a conductive agent and/or a binder.
  • the conductive agent may include superconducting carbon, acetylene black, carbon black, At least one of piano black, carbon dots, carbon nanotubes, graphene and carbon nanofibers;
  • the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polyte
  • the positive electrode current collector has two surfaces facing each other in its thickness direction, and the positive electrode active material layer is disposed on any one or both of the two facing surfaces of the positive electrode current collector.
  • the present application does not particularly limit the preparation method of the positive electrode sheet, and the positive electrode sheet can be prepared by referring to the existing method.
  • the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode sheet is formed by drying and cold pressing.
  • the positive electrode slurry can be formed by dispersing the components such as the positive electrode active material, the optional conductive agent, and the optional binder in a solvent (such as N-methylpyrrolidone) and stirring them evenly.
  • the positive electrode sheet of the present application does not exclude other additional functional layers in addition to the positive electrode active material layer.
  • the positive electrode sheet may also include a conductive primer layer (e.g., composed of a conductive agent and a binder) disposed between the positive electrode current collector and the positive electrode active material layer.
  • the positive electrode sheet may also include a protective layer covering the surface of the positive electrode active material layer.
  • the present application proposes a battery, comprising the aforementioned positive electrode plate, the positive electrode plate comprising a positive electrode collector and a positive electrode active material layer located at least on one side of the positive electrode collector, the positive electrode active material layer comprising the aforementioned positive electrode active material, and/or, the positive electrode active material prepared by the aforementioned method.
  • the battery may be a secondary battery.
  • the battery 5 in FIG. 2 may be a sodium ion battery or the like.
  • the battery includes a positive electrode sheet, a negative electrode sheet, and a separator.
  • active ions are embedded and extracted back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays a role in conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet, which can prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
  • the electrode assembly includes a positive electrode sheet, a negative electrode sheet, and a separator located between the positive electrode sheet and the negative electrode sheet.
  • the electrode assembly is a winding structure.
  • the positive electrode sheet and the negative electrode sheet are wound to form a winding structure.
  • the electrode assembly is a laminate structure.
  • a plurality of positive electrode sheets and a plurality of negative electrode sheets may be provided respectively, and the plurality of positive electrode sheets and the plurality of negative electrode sheets may be alternately stacked.
  • a plurality of positive electrode sheets may be provided, and the negative electrode sheet is folded to form a plurality of stacked folded segments, with a positive electrode sheet sandwiched between adjacent folded segments.
  • both the positive electrode sheet and the negative electrode sheet are folded to form a plurality of stacked folded sections.
  • a plurality of separators may be provided, each of which is provided between any adjacent positive electrode sheets or negative electrode sheets.
  • the separator may be disposed continuously, and disposed between any adjacent positive electrode sheets or negative electrode sheets by folding or winding.
  • the shape of the electrode assembly can be cylindrical, flat, or polygonal.
  • the electrode assembly is provided with tabs, which can lead current out of the electrode assembly.
  • the tabs include a positive tab and a negative tab.
  • the positive electrode plate can be the positive electrode plate described above.
  • the negative electrode plate may include a negative electrode current collector
  • the negative electrode current collector may be a metal foil, a foam metal, or a composite current collector.
  • the metal foil may include aluminum or stainless steel treated with silver, stainless steel, copper, aluminum, nickel, carbon electrode, or titanium.
  • the foam metal may include foam nickel, foam copper, foam aluminum, foam alloy, or foam carbon.
  • the composite current collector may include a polymer material base and a metal layer.
  • the composite current collector may be formed by mixing a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy, etc.) It is formed on a polymer material substrate (such as a substrate of polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyethylene, etc.).
  • a metal material copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy, etc.
  • a polymer material substrate such as a substrate of polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyethylene, etc.
  • the negative electrode plate may be a rolled metal foil or a surface-coated inert layer of metal powder coated on a current collector.
  • the negative electrode current collector may be a composite current collector, for example, the composite current collector may include at least one of carbon cloth, carbon film, carbonaceous material, porous current collector, alloyed modified current collector, lithium-philic modified current collector and sodium-philic modified current collector.
  • the negative electrode plate may include a negative electrode current collector and a negative electrode active material layer arranged on at least one side of the negative electrode current collector, the negative electrode active material layer may include a negative electrode active material, and the negative electrode active material may be a material with a high gram capacity.
  • the negative electrode active material may include at least one of natural graphite, artificial graphite, soft carbon, hard carbon, silicon-based material, tin-based material, and lithium titanate.
  • the silicon-based material may include at least one of elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy material;
  • the tin-based material may include at least one of elemental tin, tin oxide, and tin alloy material.
  • the present application has no particular limitation on the type of isolation membrane, and any porous isolation membrane with good chemical stability and mechanical stability can be selected.
  • the main material of the separator may include at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, ceramic and polyvinylidene fluoride.
  • the separator may be a single-layer film or a multi-layer composite film. When the separator is a multi-layer composite film, the materials of each layer may be the same or different.
  • the separator may be a separate component located between the positive electrode sheet and the negative electrode sheet, or it may be attached to the surface of the positive electrode sheet and/or the negative electrode sheet.
  • the positive electrode sheet, the negative electrode sheet and the separator can be wound or laminated to form an electrode assembly 52.
  • the electrode assembly 52 is encapsulated in the receiving cavity, and the electrolyte fills the internal space of the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the electrolyte can be selected with reference to existing secondary batteries.
  • the electrolyte includes an organic solvent, a sodium salt and an optional additive.
  • the sodium salt includes, but is not limited to, at least one of NaPF 6 , NaClO 4 , NaBCl 4 , NaSO 3 CF 3 and Na(CH 3 )C 6 H 4 SO 3 .
  • the organic solvent includes, but is not limited to, at least one of 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), 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
  • the additives in the electrolyte may include negative electrode film-forming additives and positive electrode film-forming additives; they may also include additives that can improve certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high temperature and/or low temperature performance of the battery, etc.
  • the additives may include at least one of vinylene carbonate (VC), vinyl carbonate (VEC), vinyl sulfate (DTD), propylene sulfate, vinyl sulfite (ES), 1,3-propane sultone (PS), 1,3-propylene sultone (PST), sulfonate cyclic quaternary ammonium salt, succinic anhydride, succinonitrile (SN), adiponitrile (AND), tris(trimethylsilyl) phosphate (TMSP) and tris(trimethylsilyl) borate (TMSB).
  • VC vinylene carbonate
  • VEC vinyl carbonate
  • DTD vinyl sulfate
  • ES vinyl sulfite
  • PS 1,3-propane sultone
  • PST 1,3-propylene sultone
  • succinic anhydride succinonitrile
  • SN succinonitrile
  • AND adiponitrile
  • TMSP tri
  • FIG. 2 is a square-structured battery 5 as an example.
  • the outer packaging of the battery 5 may include a shell 51 and a top cover assembly 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate are enclosed to form a receiving cavity.
  • the shell 51 has There is an opening communicating with the accommodating cavity, and the top cover assembly 53 can cover the opening to close the accommodating cavity.
  • batteries can be assembled into battery modules, and the number of batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • Figure 4 is a battery module 4 as an example.
  • the battery 5 shown in Figure 2 can be used as a battery cell, and a plurality of battery cells can be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner.
  • the plurality of battery cells can further be fixed by fasteners.
  • the battery module 4 can also include a housing having a housing space, and a plurality of battery cells are accommodated in the housing space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • Figures 5 and 6 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 arranged in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery module 4.
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application proposes an electric device, comprising the aforementioned battery 5. Therefore, the electric device has all the features and advantages of the aforementioned battery 5, which will not be described in detail here.
  • Batteries, battery modules, or battery packs can be used as power sources for electrical devices, or as energy storage units for electrical devices.
  • Electrical devices may include mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto. Electrical devices may select batteries, battery modules, or battery packs according to their usage requirements.
  • FIG7 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module can be used.
  • the power-consuming device may also be a mobile phone, a tablet computer, a laptop computer, etc.
  • a mobile phone a tablet computer, a laptop computer, etc.
  • Such a device is usually required to be light and thin, and a battery may be used as a power source.
  • a total of 30 g of Na 2 CO 3 , Mn 2 O 3 , and NiO were weighed according to a Na:Mn:Ni molar ratio of 0.75:0.8:0.2.
  • the obtained sample was pre-ground in an agate mortar and then added to a planetary ball mill for ball milling for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 850°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 850°C for 15 hours. After natural cooling, the first sodium manganese oxide Na 0.7 Mn 0.8 Ni 0.2 O 2 was obtained.
  • a total of 30 g of Na 2 CO 3 , Mn 2 O 3 , Fe 2 O 3 , NiO, and CuO were weighed according to a Na:Mn:Fe:Ni:Cu molar ratio of 0.95:0.4:0.3:0.2:0.1.
  • the obtained sample was pre-ground in an agate mortar and then added to a planetary ball mill for 1 hour to obtain Precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 950°C in a muffle furnace at a heating rate of 5°C/min, and kept at 950°C for 15 hours. After natural cooling, the second sodium manganese oxide Na 0.9 Mn 0.4 Fe 0.3 Ni 0.2 Cu 0.1 O 2 was obtained.
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide obtained above were sampled at a molar ratio of 1:3.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide in Example 2 is the same as the synthesis method of the first sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of Na 2 CO 3 , Mn 2 O 3 , Fe 2 O 3 , NiO and TiO 2 were weighed according to a Na:Mn:Fe:Ni:Ti molar ratio of 0.95:0.4:0.3:0.2:0.1.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for ball milling for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 950°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 950°C for 15 hours. After cooling naturally, the second sodium manganese oxide Na 0.9 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.1 O 2 was obtained.
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide were sampled at a molar ratio of 1:9.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide in Example 3 is the same as the synthesis method of the first sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of Na 2 CO 3 , Mn 2 O 3 , Fe 2 O 3 , NiO and ZnO were weighed according to a Na:Mn:Fe:Ni:Zn molar ratio of 0.95:0.4:0.3:0.2:0.1.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 950°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 950°C for 15 hours. After cooling naturally, the second sodium manganese oxide Na 0.9 Mn 0.4 Fe 0.3 Ni 0.2 Zn 0.1 O 2 was obtained.
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide obtained above were sampled at a molar ratio of 1:3.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 4 is the same as the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide obtained above were sampled at a molar ratio of 1:4.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 5 is the same as the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide were sampled at a molar ratio of 3:1.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 6 is the same as the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 2. The difference is that:
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide were sampled at a molar ratio of 0.5:99.5.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 800°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 800°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Comparative Example 1 is the same as the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide were sampled at a molar ratio of 1:3.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 300°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 300°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Comparative Example 2 is the same as the synthesis method of the first sodium manganese oxide and the second sodium manganese oxide in Example 1. The difference is that:
  • a total of 30 g of the first sodium manganese oxide and the second sodium manganese oxide were sampled at a molar ratio of 1:3.
  • the obtained sample was pre-ground in an agate mortar and added to a planetary ball mill for 1 hour to obtain a precursor mixture.
  • the obtained precursor mixture was evenly placed in an open crucible, and then heated from room temperature to 1000°C in a muffle furnace at a heating rate of 5°C/min, and kept at a constant temperature of 1000°C for 10 hours. After natural cooling, the positive electrode active material was obtained.
  • Comparative Example 3 only includes the first sodium manganese oxide in Example 1.
  • Comparative Example 4 only includes the second sodium manganese oxide in Example 1.
  • the sample to be tested was ground in an agate mortar and passed through a 350 mesh sieve. An appropriate amount of the sieved sample was placed in the middle of the groove of the sample rack so that the loose sample powder was slightly higher than the plane of the sample rack. A glass slide was used to gently press the surface of the sample to make the surface of the sample flat and consistent with the plane of the frame, and the excess powder was scraped off.
  • a Brucker D8A_A25 X-ray powder diffractometer from Brucker AxS, Germany, was used with CuK ⁇ rays as the radiation source and the wavelength of the ray was 2.34mm. The test was performed with a scanning 2 ⁇ angle range of 5°-60° and a scanning rate of 4°/min.
  • the 2 ⁇ angle peak position is generally within 15°-17° through the angle corresponding to the 002 crystal plane.
  • the 2 ⁇ angle peak is generally within 15°-17° through the angle corresponding to the 003 crystal plane.
  • the diffraction peak intensity S 2 corresponding to the 003 crystal plane within the range of 15°-17° is obtained through full spectrum fitting Rietveld.
  • the instrument standard refers to EPA6010D-2014 "Inductively Coupled Plasma Atomic Emission Spectrometry".
  • the sample is treated by chemical methods to be digested into a solution, atomized into plasma and excited to produce characteristic spectral lines of the elements.
  • the element content is qualitatively and quantitatively analyzed based on the wavelength and intensity of the spectral lines (which are proportional to the concentration).
  • the positive electrode active material is prepared into a button cell, and then the button cell is charged to 4.3V at a current density of 10 mA/g, and then discharged to 2.0V at a current density of 10 mA/g, to obtain the discharge specific capacity C 0 of the button cell, and then the charge and discharge are cycled at a current density of 10 mA/g for 50 cycles, and the discharge specific capacity C 1 of the 50th cycle is obtained.
  • the capacity retention rate of the sodium manganese oxide positive electrode active material after 50 cycles (C 1 /C 0 ) ⁇ 100%.
  • the button cell is prepared according to the steps shown below.
  • Preparation of positive electrode sheets Add positive electrode active material, conductive agent carbon black (Super P), and binder polyvinylidene fluoride (PVDF) in a mass ratio of 80:15:5 into N-methylpyrrolidone (NMP) and stir evenly to form positive electrode slurry; evenly apply the positive electrode slurry on the surface of the positive electrode current collector aluminum foil, and after drying and cold pressing, punch it into a disc with a diameter of 14 mm to obtain a positive electrode sheet.
  • NMP N-methylpyrrolidone
  • Negative electrode Sodium metal sheet is used.
  • Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in equal volumes to obtain an organic solvent, and then NaClO 4 was dissolved in the above organic solvent to prepare an electrolyte with a concentration of 1 mol/L.
  • Isolation membrane A porous polyethylene membrane is used as the isolation membrane.
  • Preparation of button battery stack the above-mentioned positive electrode sheet, separator, and negative electrode sheet in order, so that the separator is between the positive electrode sheet and the negative electrode sheet, add the above-prepared electrolyte, and the preparation of the button battery is completed.

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Abstract

本申请公开了正极活性材料及其制备方法、正极极片、电池和用电装置，正极活性材料包括钠锰氧化物，钠锰氧化物包括第一相和第二相，第一相包括依次交替的第一钠离子层和第一过渡金属层，第二相包括依次交替的第二钠离子层和第二过渡金属层；第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。

Description

正极活性材料及其制备方法、正极极片、电池和用电装置 技术领域
本公开涉及电池领域，具体而言，涉及正极活性材料及其制备方法、正极极片、电池和用电装置。
背景技术
钠离子电池主要是依靠钠离子在正负极之间的运动来工作的二次电池。以钠离子电池为代表的二次电池已在储能电源系统(如水力、火力、风力和太阳能电站等)以及电动车辆、航空航天等多个领域得到应用。相较于锂离子电池，作为钠离子电池正极活性材料主要组成的钠盐的储量更丰富，钠盐价格也远低于作为锂离子电池正极活性材料主要组成的锂盐价格，从而使得钠离子电池在原材料方面拥有显著的成本优势。然而，钠离子电池仍存在能量密度低、稳定性不佳等问题，导致钠离子电池在实际应用受到限制。
申请内容
在本申请的第一方面，本申请提出了一种正极活性材料，包括钠锰氧化物，所述钠锰氧化物包括第一相和第二相，所述第一相包括依次交替的第一钠离子层和第一过渡金属层，所述第二相包括依次交替的第二钠离子层和第二过渡金属层；所述第一相中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，所述第二相中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。由此，可以使得第一相和第二相在脱嵌钠过程中发生的应变较小，减少晶体结构上缺陷和裂纹的出现，进而提高正极活性材料的循环稳定性。
根据本申请的实施例，所述钠锰氧化物包括掺杂元素Q，所述掺杂元素满足以下条件的至少之一：所述掺杂元素Q包括第一掺杂元素Q1，所述第一掺杂元素部分取代所述钠锰氧化物中的钠元素，所述第一掺杂元素包括Li、K、Ca、La、Sr中的至少一种；所述掺杂元素Q包括第二掺杂元素Q2，所述第二掺杂元素部分取代所述钠锰氧化物中的锰元素，所述第二掺杂元素包括Fe、Co、Ni、Cu、Zn、Ga、Li、B、Mg、Al、Si、Ti、Y、Zr、Nb、Mo、In、Sn、Sb、La、Ce、Ta、W、Bi中的至少一种；所述掺杂元素Q包括第三掺杂元素Q3，所述第三掺杂元素部分取代所述钠锰氧化物中的氧元素，所述第三掺杂元素包括F、Cl中的至少一种。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
根据本申请的实施例，所述钠锰氧化物满足化学式：NaxQ1aMnyQ2bOzQ3c，其中，0.5<x≤1.2，0≤a≤0.5，0.5<x+a≤1.2；0<y，0≤b≤0.6，y+b＝1；1.8≤z≤2.2，0≤c≤0.2，1.8≤z+c≤2.2。由此，可以提高正极活性材料在循环过程中的结构稳定性。
根据本申请的实施例，所述钠锰氧化物满足化学式：NaxQ1aMnyFedNieQ2bOzQ3c，其中，y+d+e+b＝1，0.1≤d≤0.6，0.1≤e≤0.6，所述第一相中所述第一过渡金属层/所述第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，所述第二相中所述第二过渡金属层/所述第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，其中，S1/(S2+S1)×e≤0.1。由此，可以提高正极活性材料的比容量、放电平均电压以及在循环过程中的结构稳定性。
根据本申请的实施例，0.05≤S1/(S2+S1)，可选地，0.1≤S1/(S2+S1)。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
根据本申请的实施例，所述钠锰氧化物中的所述第一相满足化学式：Nax1Q1a1Mny1Fed1Nie1Q2b1OzQ3c1，其中，0.6<x1≤0.8，0≤a1≤0.6，0≤b1≤0.6，y1+d1+e1+c1＝1，且0≤(d1×e1)/(y12)≤0.5；所述钠锰氧化物中的所述第二相满足化学式：Nax2Q1a2Mny2Fed2Nie2Q2b2OzQ3c2，其中，0.7<x2≤1，0.1≤a2≤0.6，0.1≤b2≤0.6，y2+d2+e2+c2＝1，且0.1≤(d2×e2)/(y22)≤1。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
根据本申请的实施例，所述第一相中所述过第一渡金属层/所述第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，所述第二相中所述第二过渡金属层/所述第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，S1和S2满足0.01≤S1/(S1+S2)≤0.5。由此，正极活性材料在具有较高循环稳定性的同时，还可以具有较高的比容量。可选地，0.05≤S1/(S1+S2)≤0.5。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
根据本申请的实施例，0.550nm≤d1≤0.565nm，0.530nm≤d2≤0.545nm。由此，可以利用第一相和第二相在循环过程中的协同作用，提高正极活性材料在循环过程中的结构稳定性。
根据本申请的实施例，所述第一相为P2相，空间群为P63/mmc；所述第二相为O3相，空间群为R3m。由此，利用P2相与O3相之间的协同效应，可进一步提高正极活性材料的循环稳定性和比容量。
根据本申请的实施例，在25℃下，质量浓度为2g/18mL所述正极活性材料的去离子水溶液的pH为7-13；可选地，pH为11-13。由此，有利于形成分散均匀、易于涂布的正极浆料。
在本申请的第二方面，本申请提出了一种制备前述的正极活性材料的方法，包括：提供前驱体；对所述前驱体进行煅烧处理，以获得所述正极活性材料，其中，所述正极活性材料包括钠锰氧化物，所述钠锰氧化物包括第一相和第二相，所述第一相包括依次交替的第一钠离子层和第一过渡金属层；所述第二相包括依次交替的第二钠离子层和第二过渡金属层；所述第一相中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，所述第二相中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。由此，可以通过较为简便的方法制得前述的正极活性材料。
根据本申请的实施例，所述提供前驱体包括：提供第一钠锰氧化物和第二钠锰氧化物的混合物，所述混合物中所述第一钠锰氧化物的摩尔数为m1，所述混合物中所述第二钠锰氧化物的摩尔数为m2，m1:m2＝(1:2)-(1:10)，其中，所述第一钠锰氧化物中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为0.550nm-0.565nm，所述第二钠锰氧化物中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为0.530nm-0.545nm。由此，可以通过两步煅烧工艺获得前述的正极活性材料，精准调控第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距d1，以及第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距d2。
根据本申请的实施例，所述煅烧处理满足以下条件的至少之一：所述煅烧处理的温度为800℃-900℃；所述煅烧处理的时间为0.5h-20h。由此，可以获得所需层间距的正极活性材料。
根据本申请的实施例，提供第一钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第一煅烧处理，所述混合物中所述钠源的摩尔数为m1-1，所述混合物中所述锰氧化物的摩尔数为 m2-1，所述混合物中所述掺杂元素氧化物的摩尔数为m3-1，m1-1:m2-1:m3-1＝(0.5-0.8):(0.6-0.95):(0-0.4)。由此，可以获得所需层间距的第一钠锰氧化物。
根据本申请的实施例，所述第一煅烧处理满足以下条件的至少之一：所述第一煅烧处理的温度为700℃-900℃；所述第一煅烧处理的时间为10h-20h。
根据本申请的实施例，提供第二钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第二煅烧处理，所述混合物中所述钠源的摩尔数为m1-2，所述混合物中所述锰氧化物的摩尔数为m2-2，所述混合物中所述掺杂元素氧化物的摩尔数为m3-2，m1-2:m2-2:m3-2＝(0.8-1.1):(0.3-0.5):(0-0.6)。由此，可以获得所需层间距的第二钠锰氧化物。
根据本申请的实施例，所述第二煅烧处理满足以下条件的至少之一：所述第二煅烧处理的温度为800℃-1100℃；所述第二煅烧处理的时间为10h-20h。
在本申请的第三方面，本申请提出了一种正极极片，包括前述的正极活性材料，和/或，采用前述的方法制备得到的正极活性材料。由此，该正极极片具有前述正极活性材料和制备正极活性材料的方法的全部特征及优点，在此不再赘述。
在本申请的第四方面，本申请提出了一种电池，包括前述的正极极片。由此，该电池具有前述正极极片的全部特征及优点，在此不再赘述。
在本申请的第五方面，本申请提出了一种用电装置，包括前述的电池。由此，该用电装置具有前述电池的全部特征及优点，在此不再赘述。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施方式的描述中将变得明显和容易理解。附图仅用于示出实施方式的目的，而并不认为是对本申请的限制。其中，
图1为钠锰氧化物的层间距示意图；
图2显示了根据本申请一个实施例的电池的示意图；
图3是图2所示的本申请一实施例的电池的爆炸图；
图4显示了根据本申请一个实施例的电池模块的示意图；
图5显示了根据本申请一个实施例的电池包的示意图；
图6是图5所示的本申请一个实施例的电池包的爆炸图；
图7显示了根据本申请一个实施例的电池用作电源的用电装置的示意图；
图8显示了本申请实施例1中正极活性材料的XRD衍射谱图；
图9显示了本申请对比例1中正极活性材料的XRD衍射谱图。
附图标记说明：
1：电池包，2：上箱体，3：下箱体，4：电池模块，5：电池，
51：壳体，52：电极组件，53顶盖组件。
具体实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。
在本申请的描述中，“A和/或B”可以包括单独A的情况，单独B的情况，A和B的情况的任一种，其中A、B仅用于举例，其可以是本申请中使用“和/或”连接的任意技术特征。
在本申请的描述中，“多个”的含义是两个或两个以上。
在本申请的描述中，无论是否使用“大约”或“约”等字眼，所有在此公开了的数字均为近似值。每一个数字的数值有可能会出现10％以下的差异或者本领域人员认为的合理的差异，如1％、2％、3％、4％或5％的差异。
除非另有定义，本申请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；本申请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；除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测量方法进行测量(例如，可以按照在本申请的实施例中给出的方法进行测试)。
本申请的说明书和权利要求书中的术语“包括”和“具有”以及它们的任何变形为开放式表达，即包括本申请所指明的内容，但并不排除其它方面的内容。
随着动力电池应用领域的不断扩大，动力电池市场的需求量也在不断地扩增。以钠离子电池为代表的二次电池已经在储能电源系统以及电动车辆、航空航天等多个领域得到应用。目前的钠离子电池存在随着充放电循环次数的增加，循环性能显著下降，以及正极活性材料失活导致电池容量的下降的问题。
以含有钠锰氧化物的正极活性材料为例，层状结构的钠锰氧化物在充放电循环过程中会持续发生钠离子的脱嵌，相应地，在钠离子的脱嵌过程中，钠锰氧化物的层状结构会发生收缩和膨胀以完成钠离子的脱嵌。当钠锰氧化物的层状结构在收缩和膨胀的过程中所受到的应力过大时，钠锰氧化物层状结构会被过大的应力破坏，导致钠锰氧化物颗粒内部出现缺陷和裂纹，进而导致正极活性材料循环稳定性较差。
基于以上考虑，本申请提出了具有混合相的钠锰氧化物正极活性材料，该正极活性材料中第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距d1，以及第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距d2，d1与d2之间差值在0.01nm到0.02nm之间，从而在钠锰氧化物层状结构的收缩和膨胀的过程中会起到“互锁”的作用，使得钠锰氧化物层状结构在脱嵌钠过程中所受到的应力较小，进而降低晶体结构的应变，减少晶体结构因应变过大而导致的缺陷和裂纹的出现，提高正极活性材料在充放电循环过程中的稳定性。
作为示例，参见图1，前述的层间距是指在钠锰层状氧化物中，垂直于(001)晶面方向上的相邻两层过渡金属层之间的距离。
通常情况下，电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子，例如活性钠离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
在一些实施例中，正极极片包括正极集流体和至少位于正极集流体一侧的正极活性材料层，正极活性材料层中包括正极活性材料。
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装置，或者使用具备本申请公开的电池等组成该用电装置的电源系统，或者使用电池作为储能元件的各种储能系统。用电装置可以包括手机、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。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，航天器可以包括飞机、火箭、航天飞机和宇宙飞船等。
应理解，本申请实施例描述的技术方案不仅仅局限适用于上述所描述的电池和用电装置，还可以适用于其它所有包括电池以及使用电池的用电装置，但为描述简洁，下述实施例均以电动车辆为例进行说明。
在本申请的第一方面，本申请提出了一种正极活性材料，包括钠锰氧化物，钠锰氧化物包括第一相和第二相，第一相包括依次交替的第一钠离子层和第一过渡金属层，第二相包括依次交替的第二钠离子层和第二过渡金属层；第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm，由于第一相的层间距略大于第二相的层间距，从而可以使得第一相和第二相在脱嵌钠过程中发生的应变较小，减少晶体结构上缺陷和裂纹的出现，进而提高正极活性材料的循环稳定性。
在一些实施例中，当d1-d2小于0.01nm时，第一相与第二相之间“互锁”作用不明显，无法改善正极活性材料的循环稳定性；当d1-d2大于0.02nm时，第一相与第二相之间的层间距差距过大，在充放电循环中两相之间的协同作用较差，不利于钠离子的脱嵌。
作为示例，d1-d2可以为0.01nm、0.011nm、0.012nm、0.013nm、0.014nm、0.015nm、0.016nm、0.017nm、0.018nm、0.019nm或0.02nm。
根据本申请的实施例，钠锰氧化物可以包括掺杂元素Q，由此，可以进一步提高正极活性材料的结构稳定性和比容量。
在一些实施例中，掺杂元素Q可以包括第一掺杂元素Q1，第一掺杂元素部分取代钠锰氧化物中的钠元素，第一掺杂元素包括Li、K、Ca、La、Sr中的至少一种。由此，可以提高钠离子的脱嵌速率。
在一些实施例中，掺杂元素Q可以包括第二掺杂元素Q2，第二掺杂元素部分取代钠锰氧化物中的锰元素，第二掺杂元素包括Fe、Co、Ni、Cu、Zn、Ga、Li、B、Mg、Al、Si、Ti、Y、Zr、Nb、Mo、In、Sn、Sb、La、Ce、Ta、W、Bi中的至少一种。由此，可以提高正极活性材料的比容量、平均放电电压、结构稳定性等。
在一些实施例中，掺杂元素Q可以包括第三掺杂元素Q3，第三掺杂元素部分取代钠锰氧化物中的氧元素，第三掺杂元素包括F、Cl中的至少一种。由此，可以进一步提高正极活性材料的晶体结构稳定性。
根据本申请的实施例，钠锰氧化物可以满足化学式：NaxQ1aMnyQ2bOzQ3c，其中，0.5<x≤1.2，0≤a≤0.5，0.5<x+a≤1.2；0<y，0≤b≤0.6，y+b＝1；1.8≤z≤2.2，0≤c≤0.2，1.8≤z+c≤2.2。由此，可以提高正极活性材料在循环过程中的结构稳定性。
在一些实施例中，当正极活性材料经过补钠、化成等工序，以及长期循环使用后，正极活性材料中 的钠元素的含量可能会因补钠工序出现超出标准值，也可能出现在化成和长期循环使用后低于标准值的情况；正极活性材料中氧元素的含量也可能在循环后期因晶格氧释出出现低于标准值的情况。
在一些实施例中，通过控制钠锰氧化物中各元素的含量，可以使得正极活性材料具有较高的比容量，并使得钠锰氧化物中第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距与第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距之间具有适当的差值，满足上述层间距差值的第一相和第二相之间具有协同作用，进一步提高正极活性材料的循环稳定性。
根据本申请的实施例，钠锰氧化物满足化学式：NaxQ1aMnyFedNieQ2bOzQ3c，其中，y+d+e+b＝1，0.1≤d≤0.6，0.1≤e≤0.6，第一相中第一过渡金属层/第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，第二相中第二过渡金属层/第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，其中，S1/(S2+S1)×e≤0.1。由此，可以提高正极活性材料的比容量、放电平均电压以及在循环过程中的结构稳定性。
在一些实施例中，正极活性材料中具有较大层间距的相有利于正极活性材料的高压相变，从而能有效提高正极活性材料的放电平均电压，进而提高正极活性材料的能量密度。
在另一些实施例中，正极活性材料中的Ni在充放电过程中变价能提供电荷补偿，进而提高正极活性材料的比容量。但是在充放电过程中，层间距较大的钠锰氧化物中位于过渡金属层的Ni容易迁移到钠离子层中，进而导致钠锰氧化物的层状结构被破坏，循环稳定性下降。
作为示例，当S1/(S2+S1)×e≤0.1时，正极活性材料具有较高的比容量、较高的放电平均电压，以及较优的循环稳定性。
根据本申请的实施例，0.05≤S1/(S2+S1)，可选地，0.1≤S1/(S2+S1)。由此，可以进一步提高正极活性材料的放电平均电压和循环充放电过程中的结构稳定性。
根据本申请的实施例，钠锰氧化物中的第一相满足化学式：Nax1Q1a1Mny1Fed1Nie1Q2b1OzQ3c1，其中，0.6<x1≤0.8，0≤a1≤0.6，0≤b1≤0.6，y1+d1+e1+c1＝1，且0≤(d1×e1)/(y12)≤0.5；钠锰氧化物中的第二相满足化学式：Nax2Q1a2Mny2Fed2Nie2Q2b2OzQ3c2，其中，0.7<x2≤1，0.1≤a2≤0.6，0.1≤b2≤0.6，y2+d2+e2+c2＝1，且0.1≤(d2×e2)/(y22)≤1。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
在一些实施例中，在充放电过程中，层间距较大的第一相中位于第一过渡金属层的Ni和Fe容易迁移到第一钠离子层中，进而导致钠锰氧化物的层状结构被破坏，循环稳定性下降，通过在具有较大层间距的第一相中，控制取代钠锰氧化物中的锰元素的Fe和Ni的含量相对较低，即满足0≤(d1×e1)/(y12)≤0.5，有助于使得第一相结构更加稳定，不易因Fe和Ni的迁移而被破坏，提高正极活性材料在充放电循环过程中的结构稳定性。
在一些实例中，由于在具有较小层间距的第二相中位于第二过渡金属层的Fe和Ni不容易发生迁移，通过控制Fe和Ni的含量相对较高，即0.1≤(d1×e1)/(y12)≤1，可提高正极活性材料的比容量。
根据本申请的实施例，第一相中第一过渡金属层/第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，第二相中第二过渡金属层/第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，S1和S2满足0.01≤S1/(S1+S2)≤0.5。由此，正极活性材料在具有较高循环稳定性的同时，还可以具有较高的比容量。可选地，0.05≤S1/(S1+S2)≤0.5。由此，可以进一步提高正极活性材料的结构稳定性和比容量。
作为示例，正极活性材料中过渡金属层/钠离子层在特定2θ范围内X射线的衍射峰强是指：在正极 活性材料中相邻的过渡金属层与钠离子层共同形成的晶体结构在特定2θ范围内对X射线的衍射峰强。
作为示例，第一相中第一过渡金属层/第一钠离子层对X射线的衍射峰强S1、第二相中第二过渡金属层/第二钠离子层对X射线的衍射峰强S2可以通过如下方法测试得到：对正极活性材料进行XRD测试，以CuKα射线为辐射源，射线波长扫描2θ角范围为5°-60°，扫描速率为4°/min进行测试，其中，2θ角峰位在15°-17°内，通过全谱拟合Rietveld分峰后即可得到各自的衍射峰强，一般地，正极活性材料在2θ为13°-16.2°内对X射线的衍射峰强即为S1，正极活性材料在2θ为16.2°-17°内对X射线的衍射峰强即为S2。
作为示例，针对第一相，在前述XRD测试完成后通过002晶面对应的角度，一般2θ角峰位在15°-17°内，根据布拉格方程2dsinθ＝λ，以及002晶面每个晶胞包含三层第一过渡金属层，即可得到002晶面的层间距d002；针对第二相，在测试完成后通过003晶面对应的角度，一般2θ角峰位在15°-17°内，根据布拉格方程2dsinθ＝λ，以及003晶面每个晶胞包含三层第二过渡金属层，即可得到003晶面的层间距d003。通过d002和d003即可以得到对应的第一相和第二相中相邻的过渡金属层在垂直于(001)晶面方向上的层间距。
根据本申请的实施例，0.550nm≤d1≤0.565nm，0.530nm≤d2≤0.545nm。由此，可以利用第一相和第二相在循环过程中的协同作用，提高正极活性材料在循环过程中的结构稳定性。
作为示例，正极活性材料的元素组成可以采用电感耦合等离子体发射光谱法测试，具体地，仪器标准参考EPA6010D-2014《电感耦合等离子体原子发射光谱法》。将待测样品经过化学方法处理消解成溶液后，雾化进入等离子体被激发出元素的特征谱线，根据谱线的波长和强度(与浓度成正比)来定性和定量分析元素含量。其中，正极活性材料中两相各自的组成可以通过对待测样品进行离子抛光截面后，对不同相的颗粒进行元素分析得到。
根据本申请的实施例，第一相为P2相，空间群为P63/mmc；第二相为O3相，空间群为R3m。由于P2相与O3相之间的氧层排列不一致，有助于提高第一相与第二相之间的“互锁”效应，从而可进一步提高正极活性材料的循环稳定性。
作为示例，通过将正极活性材料的XRD衍射峰与XRD分析软件的标准卡片对比，即可确认正极活性材料的空间群。
根据本申请的实施例，在25℃下，质量浓度为2g/18mL的正极活性材料的去离子水溶液的pH可以为7-13；可选地，pH为11-12.5。
作为示例，正极活性材料的正极活性材料的pH值可以为7、7.5、8、8.5、9、9.5、10、10.5、11、11.5、12、12.5或13。
作为示例，正极活性材料可以呈弱碱性，从而有易于后续形成适用于涂布的正极浆料，正极活性材料的pH为7-13。可选地，正极活性材料的pH可以满足11-13，进一步地，正极活性材料的pH可以满足11-12.5，从而可以减少调浆过程中的凝胶现象的产生，提高正极浆料的涂布稳定性。
作为示例，本申请的正极活性材料的pH通过如下方法测得：通过ICP确定正极活性材料的元素组成后，取质量2g正极活性材料加入到18mL去离子水中，在室温(25℃)下搅拌至完全溶解后，静置30min，对所得上清液的pH进行测试，测得的pH结果即为该正极活性材料的pH。
在本申请的第二方面，本申请提出了一种制备前述的正极活性材料的方法，包括：提供前驱体；对前驱体进行煅烧处理，以获得正极活性材料，其中，正极活性材料包括钠锰氧化物，钠锰氧化物包括第一相和第二相，第一相包括依次交替的第一钠离子层和第一过渡金属层；第二相包括依次交替的第二钠离子层和第二过渡金属层；第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。由此，可以通过较为简便的方法制得前述的正极活性材料。
根据本申请的实施例，提供前驱体包括：提供第一钠锰氧化物和第二钠锰氧化物的混合物，混合物中第一钠锰氧化物的摩尔数为m1，混合物中第二钠锰氧化物的摩尔数为m2，混合物中第一钠锰氧化物与第二钠锰氧化物的摩尔比m1:m2＝(1:2)-(1:10)，其中，第一钠锰氧化物中相邻的过渡金属层在垂直于(001)晶面方向上的层间距为0.550nm-0.565nm，第二钠锰氧化物中相邻的过渡金属层在垂直于(001)晶面方向上的层间距为0.530nm-0.545nm。由此，可以通过两步煅烧工艺获得前述的正极活性材料，精准调控第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距和第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距。
根据本申请的实施例，煅烧处理满足以下条件的至少之一：煅烧处理的温度可以为800℃-900℃；煅烧处理的时间可以为0.5h-20h。
作为示例，对于第一钠锰氧化物和第二钠锰氧化物的混合物进行煅烧处理的温度可以为800℃、810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃或900℃。
当对于第一钠锰氧化物和第二钠锰氧化物的混合物进行煅烧处理的温度为800℃-900℃时，可以较为精准地调控正极活性材料中第一相中相邻的第一过渡金属层在垂直于(001)晶面方向上的层间距d1，以及第二相中相邻的第二过渡金属层在垂直于(001)晶面方向上的层间距d2，使得d1与d2之间的差值位于前述的范围内，从而在钠锰氧化物层状结构的收缩和膨胀的过程中第一相与第二相之间会起到“互锁”的作用，使得钠锰氧化物层状结构在脱嵌钠过程中所受到的应力较小，进而降低晶体结构的应变，减少晶体结构因应变过大而导致的缺陷和裂纹的出现，提高正极活性材料在充放电循环过程中的稳定性。
作为示例，对于第一钠锰氧化物和第二钠锰氧化物的混合物进行煅烧处理的时间可以为0.5h、1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h。
根据本申请的实施例，提供第一钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第一煅烧处理，混合物中钠源的摩尔数为m1-1，混合物中锰氧化物的摩尔数为m2-1，混合物中掺杂元素氧化物的摩尔数为m3-1，m1-1:m2-1:m3-1＝(0.5-0.8):(0.6-0.95):(0-0.4)。由此，可以获得所需层间距的第一钠锰氧化物。
根据本申请的实施例，第一煅烧处理满足以下条件的至少之一：第一煅烧处理的温度可以为700℃-900℃；第一煅烧处理的时间可以为10h-20h。
作为示例，合成第一钠锰氧化物时进行第一煅烧处理的温度可以为700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃、810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃或900℃。
作为示例，合成第一钠锰氧化物时进行第一煅烧处理的时间可以为10h、11h、12h、13h、14h、15h、 16h、17h、18h、19h或20h。
在一些实施例中，在前述的钠源、锰氧化物、掺杂元素氧化物配比，以及第一煅烧处理的条件下，即可以得到相邻的过渡金属层在垂直于(001)晶面方向上的层间距为0.550nm-0.565nm的第一钠锰氧化物。
根据本申请的实施例，提供第二钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第二煅烧处理，混合物中钠源的摩尔数为m1-2，混合物中锰氧化物的摩尔数为m2-2，混合物中掺杂元素氧化物的摩尔数为m3-2，m1-2:m2-2:m3-2＝(0.8-1.1):(0.3-0.5):(0-0.6)。
根据本申请的实施例，第二煅烧处理满足以下条件的至少之一：第二煅烧处理的温度为800℃-1100℃；第二煅烧处理的时间为10h-20h。
作为示例，合成第二钠锰氧化物时进行第二煅烧处理的温度可以为800℃、810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃、900℃、910℃、920℃、930℃、940℃、950℃、960℃、970℃、980℃、990℃、1000℃、1010℃、1020℃、1030℃、1040℃、1050℃、1060℃、1070℃、1080℃、1090℃或1100℃。
作为示例，合成第二钠锰氧化物时进行第二煅烧处理的时间可以为10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h。
在一些实施例中，在前述的钠源、锰氧化物、掺杂元素氧化物配比，以及第二煅烧处理的条件下，即可以得到相邻的过渡金属层在垂直于(001)晶面方向上的层间距为0.530nm-0.545nm的第二钠锰氧化物。
作为示例，钠源可以包括Na2CO3、NaHCO3、NaOH、Na2O2中的至少一种。
作为示例，锰氧化物可以包括Mn2O3、Mn3O4、MnO、MnO2中的至少一种。
需要说明的是，上述制备正极活性材料的方法中的相关参数可以参考前述实施例中的部分或全部技术特征，该制备正极活性材料的方法相关实施例未描述的部分，也可以参考前述实施例及相关附图，在此不再赘述。
上文对各个实施例的描述倾向于强调各个实施例之间的不同之处，其相同或相似之处可以相互参考，为了简洁，本文不再赘述。
在本申请的第三方面，本申请提出了一种正极极片，包含前述的正极活性材料，和/或采用前述的方法制备的正极活性材料。
在一些实施方式中，正极极片包括正极集流体以及设置在正极集流体至少一侧的正极活性材料层，正极活性材料层包含正极活性材料。
在本申请中，正极集流体可以为金属箔片或复合集流体。金属箔片例如为铝箔。复合集流体可以包括高分子基层和形成于高分子基层至少一侧的金属层，其中，金属层的材料包括但不限于，铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等；高分子基层的高分子材料可以为聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等。
在一些实施方式中，正极活性材料是正极活性材料层中的正极活性物质，除了该正极活性材料，正极活性材料层还可选的包括导电剂和/或粘结剂。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、石墨烯和碳纳米纤维中的至少一种；粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物和含氟丙烯酸酯树脂中的至少一种。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极活性材料层设置在正极集流体相对的两个表面的任意一者或两者上。
本申请对正极极片的制备方法没有特别限定，可参照现有方法制备。例如，将正极浆料涂布在正极集流体上，经干燥、冷压形成正极极片。正极浆料可以是将正极活性材料、可选的导电剂、可选的粘结剂等组分分散于溶剂(如，N-甲基吡咯烷酮)中并搅拌均匀而形成的。
此外，本申请的正极极片并不排除除了正极活性材料层之外的其它附加功能层。例如，正极极片还可以包括设置在正极集流体和正极活性材料层之间的导电底涂层(例如由导电剂和粘结剂组成)。再例如，正极极片还包括覆盖在正极活性材料层表面的保护层。
在本申请的第四方面，本申请提出了一种电池，包括前述的正极极片，正极极片包括正极集流体和至少位于正极集流体一侧的正极活性材料层，正极活性材料层包括前述的正极活性材料，和/或，采用前述的方法制备得到的正极活性材料。
在本申请的实施例中，电池可以为二次电池。例如，图2中的电池5可以为钠离子电池等。
在一些实施例中，电池包括正极极片、负极极片以及隔离膜。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。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，可起到防止正负极短路的作用，同时可以使离子通过。
在一些实施例中，电极组件包括正极极片、负极极片以及位于正极极片和负极极片之间的隔离膜。
在一些实施例中，电极组件为卷绕结构。正极极片、负极极片卷绕形成卷绕结构。
在一些实施例中，电极组件为叠片结构。
作为示例，正极极片、负极极片可分别设置多个，多个正极极片和多个负极极片交替层叠设置。
作为示例，正极极片可设置多个，负极极片折叠形成多个层叠设置的折叠段，相邻的折叠段之间夹持一个正极极片。
作为示例，正极极片和负极极片均折叠形成多个层叠设置的折叠段。
作为示例，隔离膜可设置多个，分别设置在任意相邻的正极极片或负极极片之间。
作为示例，隔离膜可连续地设置，通过折叠或者卷绕方式设置在任意相邻的正极极片或负极极片之间。
在一些实施例中，电极组件的形状可以为圆柱状，扁平状或多棱柱状等。
在一些实施例中，电极组件设有极耳，极耳可以将电流从电极组件导出。极耳包括正极耳和负极耳。
在一些实施例中，正极极片可以为前述的正极极片。
在一些实施例中，负极极片可以包括负极集流体，负极集流体可采用金属箔片、泡沫金属或复合集流体。例如，金属箔片可以包括银表面处理的铝或不锈钢、不锈钢、铜、铝、镍、炭精电极或钛等。泡沫金属可以包括泡沫镍、泡沫铜、泡沫铝、泡沫合金、或泡沫碳等。复合集流体可以包括高分子材料基层和金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等) 形成在高分子材料基材(如聚丙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚苯乙烯、聚乙烯等的基材)上而形成。
在一些实施例中，负极极片可以为金属箔压延或表面包覆惰性层金属粉末涂敷在集流体上。
在一些实施例中，负极集流体可以为复合集流体，例如，复合集流体可以包括碳布、碳膜、碳质、多孔集流体、合金化改性集流体、亲锂改性集流体和亲钠改性集流体中的至少一种。
在一些实施例中，负极极片可以包括负极集流体以及设置在负极集流体至少一侧的负极活性材料层，负极活性材料层可以包括负极活性材料，负极活性材料可以为高克容量的材料，例如，负极活性材料可以包括天然石墨、人造石墨、软炭、硬炭、硅基材料、锡基材料、钛酸锂中至少一种。
作为示例，硅基材料可以包括单质硅、硅氧化物、硅碳复合物、硅氮复合物、硅合金材料中的至少一种；锡基材料可以包括单质锡、锡氧化物、锡合金材料中的至少一种。
本申请对隔离膜的种类没有特别的限制，可以选用任意具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
作为示例，隔离膜的主要材质可以包括玻璃纤维、无纺布、聚乙烯、聚丙烯、陶瓷及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同。隔离膜可以是单独的一个部件位于正极极片、负极极片之间，也可以附着在正极极片和/或负极极片的表面。
作为示例，参考图3，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52。电极组件52封装于容纳腔内，电解液填充电极组件52的内部空间。电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在本申请中，电解液可以参照现有的二次电池进行选择。作为示例，电解液包含有机溶剂、钠盐和可选的添加剂。钠盐包括但不限于，NaPF6、NaClO4、NaBCl4、NaSO3CF3和Na(CH3)C6H4SO3中的至少一种。有机溶剂包括但不限于，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)和二乙砜(ESE)中的至少一种。
在一些实施方式中，电解液中的添加剂可以包括负极成膜添加剂、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、改善电池高温和/或低温性能的添加剂等，作为示例，添加剂可以包括碳酸亚乙烯酯(VC)、乙烯基碳酸乙烯酯(VEC)、硫酸乙烯酯(DTD)、硫酸丙烯酯、亚硫酸乙烯酯(ES)、1,3-丙磺酸内酯(PS)、1,3-丙烯磺酸内酯(PST)、磺酸酯环状季铵盐、丁二酸酐、丁二腈(SN)、己二腈(AND)、三(三甲基硅烷)磷酸酯(TMSP)和三(三甲基硅烷)硼酸酯(TMSB)中的至少一种。
作为示例，本申请对电池的形状没有特别的限制，其可以是圆柱形、方形或其它任意的形状。例如，图2是作为一个示例的方形结构的电池5。具体地，参照图3，电池5的外包装可以包括壳体51和顶盖组件53。其中，壳体51可以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51具 有与容纳腔连通的开口，顶盖组件53能够盖设于开口，以封闭容纳腔。
作为示例，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一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。图4是作为一个示例的电池模块4。参照图4，在电池模块4中，可以采用图2中所示出的电池5作为电池单体，多个电池单体可以沿电池模块4的长度方向依次排列设置。当然，也可以按照其它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单体进行固定。电池模块4还可以包括具有容纳空间的外壳，多个电池单体容纳于该容纳空间。
作为示例，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为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。图5和图6是作为一个示例的电池包1。参照图5和图6，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
在本申请的第五方面，本申请提出了一种用电装置，包括前述的电池5。由此，该用电装置具有前述电池5的全部特征及优点，在此不再赘述。
电池、电池模块、或电池包可以用作用电装置的电源，也可以用作用电装置的能量存储单元。用电装置可以包括移动设备(例如手机、笔记本电脑等)、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、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。用电装置可以根据其使用需求来选择电池、电池模块或电池包。
作为示例，图7是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为示例，用电装置还可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用电池作为电源。
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
合成第一钠锰氧化物：
将Na2CO3、Mn2O3、NiO按照Na：Mn：Ni摩尔比为0.75：0.8：0.2称量总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至850℃，并在850℃恒温保持15h，自然降温后，即得到第一钠锰氧化物Na0.7Mn0.8Ni0.2O2。
合成第二钠锰氧化物：
将Na2CO3、Mn2O3、Fe2O3、NiO、CuO按照Na：Mn：Fe：Ni：Cu摩尔比为0.95：0.4：0.3：0.2：0.1称量总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到 前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至950℃，并在950℃恒温保持15h，自然降温后，即得到第二钠锰氧化物Na0.9Mn0.4Fe0.3Ni0.2Cu0.1O2。
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：3取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
实施例2
实施例2中第一钠锰氧化物的合成方法与实施例1中第一钠锰氧化物的合成方法相同。所不同的是，
合成第二钠锰氧化物：
将Na2CO3、Mn2O3、Fe2O3、NiO、TiO2按照Na：Mn：Fe：Ni：Ti摩尔比为0.95：0.4：0.3：0.2：0.1称量总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至950℃，并在950℃恒温保持15h，自然降温后，即得到第二钠锰氧化物Na0.9Mn0.4Fe0.3Ni0.2Ti0.1O2。
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：9取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
实施例3
实施例3中第一钠锰氧化物的合成方法与实施例1中第一钠锰氧化物的合成方法相同。所不同的是，
合成第二钠锰氧化物：
将Na2CO3、Mn2O3、Fe2O3、NiO、ZnO按照Na：Mn：Fe：Ni：Zn摩尔比为0.95：0.4：0.3：0.2：0.1称量总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至950℃，并在950℃恒温保持15h，自然降温后，即得到第二钠锰氧化物Na0.9Mn0.4Fe0.3Ni0.2Zn0.1O2。
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：3取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
实施例4
实施例4中第一钠锰氧化物、第二钠锰氧化物的合成方法与实施例1中第一钠锰氧化物、第二钠锰氧化物的合成方法相同。所不同的是，
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：4取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
实施例5
实施例5中第一钠锰氧化物、第二钠锰氧化物的合成方法与实施例1中第一钠锰氧化物、第二钠锰氧化物的合成方法相同。所不同的是，
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为3：1取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
实施例6
实施例6中第一钠锰氧化物、第二钠锰氧化物的合成方法与实施例2中第一钠锰氧化物、第二钠锰氧化物的合成方法相同。所不同的是，
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为0.5：99.5取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至800℃，并在800℃恒温保持10h，自然降温后，即得到正极活性材料。
对比例1
对比例1中第一钠锰氧化物、第二钠锰氧化物的合成方法与实施例1中第一钠锰氧化物、第二钠锰氧化物的合成方法相同。所不同的是，
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：3取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至300℃，并在300℃恒温保持10h，自然降温后，即得到正极活性材料。
对比例2
对比例2中第一钠锰氧化物、第二钠锰氧化物的合成方法与实施例1中第一钠锰氧化物、第二钠锰氧化物的合成方法相同。所不同的是，
合成正极活性材料：
按第一钠锰氧化物与第二钠锰氧化物的摩尔比为1：3取上述所得的第一钠锰氧化物和第二钠锰氧化物总计30g的样品。将所得到的样品在玛瑙研钵中预先研磨后加入到行星球磨机中球磨1h，得到前驱体混合物。将所得到的前驱体混合物均匀放置在敞口坩埚中，随后于马弗炉中以5℃/min的升温速率从室温升温至1000℃，并在1000℃恒温保持10h，自然降温后，即得到正极活性材料。
对比例3
对比例3中仅包括实施例1中的第一钠锰氧化物。
对比例4
对比例4中仅包括实施例1中的第二钠锰氧化物。
【测试部分】
1、正极活性材料表征
1)层间距、峰强度的测试
在手套箱中将待测样品在玛瑙研钵中磨细后过350目筛，取过筛后的样品适量，装入样品架凹槽中间，使松散样品粉末略高于样品架平面；取载玻片轻压样品表面，让样品表面刮平后与框架平面一致，并将多余粉末刮掉。制样完毕后，使用德国Brucker AxS公司的Brucker D8A_A25型X射线粉末衍射仪，以CuKα射线为辐射源，射线波长扫描2θ角范围为5°-60°，扫描速率为4°/min进行测试。
对于P2相，通过002晶面对应的角度，一般2θ角峰位在15°-17°内，根据2d002sinθ＝λ，得到002晶面上的层间距d002；通过全谱拟合Rietveld，得到在15°-17°范围内的002晶面对应的衍射峰强S1；
对于O3相，通过003晶面对应的角度，一般2θ角峰位在15°-17°内，根据2d003sinθ＝λ，得到003晶面上的层间距d003；通过全谱拟合Rietveld，得到在15°-17°范围内的003晶面对应的衍射峰强S2。
2)pH测试
取2g正极活性材料置于烧杯中，加入18mL去离子水并在25℃下搅拌至完全溶解，静置30min后用pH计测试上清液的pH。
3)元素组成测试
仪器标准参考EPA6010D-2014《电感耦合等离子体原子发射光谱法》。样品经过化学方法处理消解成溶液，雾化进入等离子体被激发出元素的特征谱线，根据谱线的波长和强度(与浓度成正比)来定性和定量分析元素含量。
2、性能测试
1)放电比容量测试、循环50圈容量保持率测试
25℃下，将正极活性材料制备成扣式电池后，以10mA/g的电流密度恒流充电至4.3V，再以10mA/g的电流密度恒流放电至2.0V，得到扣式电池的放电比容量C0，随后以10mA/g的电流密度恒流充放电循环50圈，取第50圈的放电比容量C1。钠锰氧化物正极活性材料循环50圈容量保持率＝(C1/C0)×100％。
其中，扣式电池按照如下所示的步骤进行制备。
正极极片的制备：将正极活性材料、导电剂炭黑(Super P)、粘结剂聚偏氟乙烯(PVDF)按照质量比80∶15∶5加入到至N-甲基吡咯烷酮(NMP)中搅拌均匀，形成正极浆料；将正极浆料均匀涂覆于正极集流体铝箔的表面上，经干燥、冷压后，冲成直径为14mm的圆片，得到正极极片。
负极极片：采用金属钠片。
电解液的制备：将碳酸乙烯酯(EC)和碳酸二乙酯(DEC)等体积混合得到有机溶剂，接着将NaClO4溶解于上述有机溶剂中，配制成浓度为1mol/L的电解液。
隔离膜：采用多孔聚乙烯膜作为隔离膜。
扣式电池的制备：将上述正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正极极片和负极极片之间，加入上述制备好的电解液，即完成扣式电池的制备。
对正极活性材料的表征结果如表1所示：
表1
其中实施例1、对比例1中正极活性材料的XRD衍射谱图可参见图8-图9。
对扣式电池的表征结果如表2所示：
表2

在本说明书的描述中，参考术语“一个实施例”、“另一个实施例”等的描述意指结合该实施例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
在本说明书的描述中，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (20)

  1. 一种正极活性材料，其中，包括钠锰氧化物，
    所述钠锰氧化物包括第一相和第二相，所述第一相包括依次交替的第一钠离子层和第一过渡金属层，所述第二相包括依次交替的第二钠离子层和第二过渡金属层；
    所述第一相中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，所述第二相中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。
  2. 根据权利要求1所述的正极活性材料，其中，所述钠锰氧化物包括掺杂元素Q，所述掺杂元素满足以下条件的至少之一：
    所述掺杂元素Q包括第一掺杂元素Q1，所述第一掺杂元素部分取代所述钠锰氧化物中的钠元素，所述第一掺杂元素包括Li、K、Ca、La、Sr中的至少一种；
    所述掺杂元素Q包括第二掺杂元素Q2，所述第二掺杂元素部分取代所述钠锰氧化物中的锰元素，所述第二掺杂元素包括Fe、Co、Ni、Cu、Zn、Ga、Li、B、Mg、Al、Si、Ti、Y、Zr、Nb、Mo、In、Sn、Sb、La、Ce、Ta、W、Bi中的至少一种；
    所述掺杂元素Q包括第三掺杂元素Q3，所述第三掺杂元素部分取代所述钠锰氧化物中的氧元素，所述第三掺杂元素包括F、Cl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，所述钠锰氧化物满足化学式：NaxQ1aMnyQ2bOzQ3c，其中，
    0.5<x≤1.2，0≤a≤0.5，0.5<x+a≤1.2；
    0<y，0≤b≤0.6，y+b＝1；
    1.8≤z≤2.2，0≤c≤0.2，1.8≤z+c≤2.2。
  4. 根据权利要求3所述的正极活性材料，其中，所述钠锰氧化物满足化学式：NaxQ1aMnyFedNieQ2bOzQ3c，其中，
    y+d+e+b＝1，0.1≤d≤0.6，0.1≤e≤0.6，
    所述第一相中所述第一过渡金属层/所述第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，所述第二相中所述第二过渡金属层/所述第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，其中，S1/(S2+S1)×e≤0.1。
  5. 根据权利要求4所述的正极活性材料，其中，0.05≤S1/(S2+S1)。
  6. 根据权利要求1-5任一项所述的正极活性材料，其中，
    所述钠锰氧化物中的所述第一相满足化学式：Nax1Q1a1Mny1Fed1Nie1Q2b1OzQ3c1，其中，
    0.6<x1≤0.8，0≤a1≤0.6，0≤b1≤0.6，y1+d1+e1+c1＝1，且0≤(d1×e1)/(y12)≤0.5；
    所述钠锰氧化物中的所述第二相满足化学式：Nax2Q1a2Mny2Fed2Nie2Q2b2OzQ3c2，其中，
    0.7<x2≤1，0.1≤a2≤0.6，0.1≤b2≤0.6，y2+d2+e2+c2＝1，且0.1≤(d2×e2)/(y22)≤1。
  7. 根据权利要求6所述的正极活性材料，其中，所述第一相中所述第一过渡金属层/所述第一钠离子层在2θ为13°-16.2°内对X射线的衍射峰强为S1，所述第二相中所述第二过渡金属层/所述第二钠离子层在2θ为16.2°-17°内对X射线的衍射峰强为S2，S1和S2满足0.01≤S1/(S1+S2)≤0.5。
  8. 根据权利要求1-7任一项所述的正极活性材料，其中，0.550nm≤d1≤0.565nm，0.530nm≤d2≤0.545nm。
  9. 根据权利要求1-8任一项所述的正极活性材料，其中，所述第一相为P2相，空间群为P63/mmc；所述第二相为O3相，空间群为
  10. 根据权利要求1-9任一项所述的正极活性材料，其中，在25℃下，质量浓度为2g/18mL的所述正极活性材料的去离子水溶液的pH为7-13。
  11. 一种制备权利要求1-10任一项所述的正极活性材料的方法，其中，包括：
    提供前驱体；
    对所述前驱体进行煅烧处理，以获得所述正极活性材料，其中，所述正极活性材料包括钠锰氧化物，
    所述钠锰氧化物包括第一相和第二相，所述第一相包括依次交替的第一钠离子层和第一过渡金属层；所述第二相包括依次交替的第二钠离子层和第二过渡金属层；所述第一相中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为d1，所述第二相中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为d2，d1-d2为0.01nm-0.02nm。
  12. 根据权利要求11所述的方法，其中，
    所述提供前驱体包括：提供第一钠锰氧化物和第二钠锰氧化物的混合物，所述混合物中所述第一钠锰氧化物的摩尔数为m1，所述混合物中所述第二钠锰氧化物的摩尔数为m2，m1:m2＝(1:2)-(1:10)，
    其中，所述第一钠锰氧化物中相邻的所述第一过渡金属层在垂直于(001)晶面方向上的层间距为0.550nm-0.565nm，所述第二钠锰氧化物中相邻的所述第二过渡金属层在垂直于(001)晶面方向上的层间距为0.530nm-0.545nm。
  13. 根据权利要求11或12所述的方法，其中，所述煅烧处理满足以下条件的至少之一：
    所述煅烧处理的温度为800℃-900℃；
    所述煅烧处理的时间为0.5h-20h。
  14. 根据权利要求12所述的方法，其中，
    提供第一钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第一煅烧处理，所述混合物中所述钠源的摩尔数为m1-1，所述混合物中所述锰氧化物的摩尔数为m2-1，所述混合物中所述掺杂元素氧化物的摩尔数为m3-1，m1-1:m2-1:m3-1＝(0.5-0.8):(0.6-0.95):(0-0.4)。
  15. 根据权利要求14所述的方法，其中，所述第一煅烧处理满足以下条件的至少之一：
    所述第一煅烧处理的温度为700℃-900℃；
    所述第一煅烧处理的时间为10h-20h。
  16. 根据权利要求12所述的方法，其中，
    提供第二钠锰氧化物包括：提供钠源、锰氧化物、掺杂元素氧化物的混合物，并进行第二煅烧处理，所述混合物中所述钠源的摩尔数为m1-2，所述混合物中所述锰氧化物的摩尔数为m2-2，所述混合物中所述掺杂元素氧化物的摩尔数为m3-2，m1-2:m2-2:m3-2＝(0.8-1.1):(0.3-0.5):(0-0.6)。
  17. 根据权利要求16所述的方法，其中，所述第二煅烧处理满足以下条件的至少之一：
    所述第二煅烧处理的温度为800℃-1100℃；
    所述第二煅烧处理的时间为10h-20h。
  18. 一种正极极片，其中，包括权利要求1-10任一项所述的正极活性材料，和/或，采用权利要求11-17任一项所述的方法制备得到的正极活性材料。
  19. 一种电池，其中，包括权利要求18所述的正极极片。
  20. 一种用电装置，其中，包括权利要求19所述的电池。
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