WO2024011486A1 - 正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置 - Google Patents

正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置 Download PDF

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WO2024011486A1
WO2024011486A1 PCT/CN2022/105646 CN2022105646W WO2024011486A1 WO 2024011486 A1 WO2024011486 A1 WO 2024011486A1 CN 2022105646 W CN2022105646 W CN 2022105646W WO 2024011486 A1 WO2024011486 A1 WO 2024011486A1
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source
active material
antimony
composite oxide
containing sodium
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French (fr)
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梁子彬
王宇豪
林文光
张欣欣
何金华
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP22937666.0A priority Critical patent/EP4336592A4/en
Priority to CN202280012930.1A priority patent/CN117716537B/zh
Priority to PCT/CN2022/105646 priority patent/WO2024011486A1/zh
Priority to US18/411,049 priority patent/US20240194867A1/en
Publication of WO2024011486A1 publication Critical patent/WO2024011486A1/zh
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • H01M4/50—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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
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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
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    • C01G53/66—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
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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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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
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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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    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 field of battery technology, and in particular to a cathode active material and its preparation method, secondary batteries, battery modules, battery packs and electrical devices.
  • lithium-ion batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields.
  • energy storage power systems such as hydraulic, thermal, wind and solar power stations
  • power tools electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields.
  • raw materials such as Ni and Co
  • Sodium-ion batteries have the advantages of abundant reserves, low cost, system safety, low temperature and high rate, and are an excellent successor to lithium-ion batteries.
  • existing sodium-ion battery cathode active materials have poor water stability and low specific capacity, which limits the development of sodium-ion batteries.
  • This application was carried out in view of the above-mentioned issues and provides a cathode active material and a preparation method thereof, a secondary battery, a battery module, a battery pack and a power device to solve the problem of poor water stability of the cathode active material in sodium ion batteries. , the problem of low specific capacity.
  • the first aspect of the present application provides a cathode active material, including a layered antimony-containing sodium composite oxide.
  • the antimony-containing sodium composite oxide has a chemical formula as shown in Formula I,
  • L is selected from Cu, Li, Ti, Zr, K, Nb, Mg, Ca, Mo, Zn, Cr, W, Bi, Sn, Ge, Al, Si, One or more of La, Ta, P and B.
  • doping with specific metal Sb can make the layered antimony-containing sodium composite oxide highly stable to water, and can effectively inhibit the antimony-containing sodium composite oxide during the electrochemical reaction process.
  • the side reaction occurs, which makes the antimony-containing sodium composite oxide have high cycle stability and can stably exert its electrochemical performance, thereby increasing the specific capacity of the sodium ion battery for the first charge and discharge.
  • the ratio of each element in the antimony-containing sodium composite oxide meets the above requirements, which can improve the orderliness of the cations in the layered structure and ensure that the positive electrode active material has high structural stability. properties, thereby making the positive active material more stable to water.
  • the antimony-containing sodium composite oxide may include higher contents of Fe and Ni, so that a sodium ion battery using such an antimony-containing sodium composite oxide cathode active material has better High first charge-discharge specific capacity. Therefore, the antimony-containing sodium composite oxide according to this embodiment better balances stability against water, cycle stability in the electrochemical process, and first charge-discharge specific capacity.
  • L is selected from one of Cu, Li, Ti, Zr, Mg, Ca, Zn, Bi, Sn, Al, Si, La, Ta, P and B or Several, optionally, L is selected from one or more of Cu, Li, Mg, Zn, Al, Si and B.
  • These specific optional additional doping elements can enhance the stability of the layered antimony-containing sodium composite oxide to water, as well as the cycling stability of the antimony-containing sodium composite oxide in electrochemical processes. Moreover, these specific optional L examples have good stability to the electrolyte and are also beneficial to the infiltration of the electrolyte.
  • the antimony-containing sodium composite oxide includes an O3 phase, and the O3 phase has a space group layered crystal structure.
  • O3 has greater advantages than other phases in both specific capacity and specific energy.
  • the antimony-containing sodium composite oxide of the present application includes an O3 phase, and the O3 phase has a space group
  • the layered crystal structure of the cathode active material with this crystal structure has good structural stability and is conducive to improving the capacity performance and cycle performance of the cathode active material.
  • the interlayer spacing of the antimony-containing sodium composite oxide is 0.53 nm to 0.54 nm.
  • the interlayer spacing (d 003 ) of the antimony-containing sodium composite oxide when the interlayer spacing (d 003 ) of the antimony-containing sodium composite oxide is controlled within this range, the structure of the cathode active material is more stable, which shows that the cycle performance of the cathode active material is better. At the same time, sodium ions are more easily deintercalated between layers, which can better improve the charge-discharge specific capacity of the cathode active material.
  • the interlayer spacing of the antimony-containing sodium composite oxide is between 0.53nm and 0.54nm, which is beneficial to the conduction and diffusion of sodium ions between layers, and can also inhibit the interaction of hydrogen ions with the layered antimony-containing sodium composite oxide when it encounters water. The sodium ions are exchanged, making the antimony-containing sodium complex oxide more stable to water.
  • the X-ray diffraction spectrum of the antimony-containing sodium composite oxide satisfies I 1 /I 0 ⁇ 0.2
  • I 1 is the peak intensity of the X-ray diffraction peak of the O3 phase 003 crystal plane of the antimony-containing sodium composite oxide after soaking in deionized water for 24 hours
  • I 0 is the antimony-containing sodium that has not been soaked in deionized water.
  • doping with antimony enhances the interaction between transition metals and oxygen in the O3 phase layered antimony-containing sodium composite oxide, thereby increasing the stability to water, which is reflected in I In terms of the 1 /I 0 parameter, the greater the ratio of I 1 /I 0 , the less sensitive it is to water, indicating that the antimony-containing sodium composite oxide is more stable to water.
  • the volume average particle size Dv50 of the positive electrode active material is 3 ⁇ m to 30 ⁇ m, optionally 5 ⁇ m to 15 ⁇ m.
  • the volume average particle size Dv50 of the cathode active material is within an appropriate range, which is conducive to obtaining a higher compaction density of the cathode active material layer and having appropriate porosity to satisfy the electrochemical reaction.
  • the required amount of electrolyte infiltration also has a shorter migration path for active ions and electrons within the particles, which can improve the energy density and cycle performance of the cathode active material layer.
  • the specific surface area of the cathode active material is 0.1m 2 /g ⁇ 5m 2 /g, optionally 0.3m 2 /g ⁇ 3m 2 /g.
  • the cathode active material has an appropriate specific surface area, which can reduce the liquid absorption phenomenon during the preparation process of the cathode slurry, improve the solid content and particle dispersion uniformity in the cathode slurry, and thereby improve the composition of the cathode slurry.
  • the particle dispersion uniformity and compaction density in the film layer of the active material further increase the specific capacity and energy density of the sodium-ion battery, and improve the cycle performance of the sodium-ion battery.
  • the tap density of the positive active material is 1g/cm 3 to 3g/cm 3 , optionally 1.5g/cm 3 to 2.5g/cm 3 .
  • the positive electrode active material has an appropriate tap density, which is beneficial to the positive electrode active material having a higher compaction density, so that the sodium ion battery has higher capacity performance and energy density.
  • the powder compaction density of the positive active material under a pressure of 8 tons is 3g/cm 3 ⁇ 5g/cm 3 , optionally 3.5g/cm 3 ⁇ 4.5g /cm 3 .
  • the positive active material has a higher compacted density, which is beneficial to the sodium-ion battery having higher capacity performance and energy density.
  • the higher the compacted density of the positive active material the higher the capacity performance and energy density of the sodium-ion battery will be.
  • the second aspect of the application also provides a method for preparing a positive active material, including:
  • the raw materials are calcined to obtain the positive active material.
  • the positive active material includes a layered antimony-containing sodium composite oxide, and the antimony-containing sodium composite oxide has a chemical formula as shown in Formula I,
  • L is selected from Cu, Li, Ti, Zr, K, Nb, Mg, Ca, Mo, Zn, Cr, W, Bi, Sn, Ge, Al, Si, One or more of La, Ta, P and B.
  • the positive electrode active material preparation method of the present application raw materials are first provided, and then the raw materials are calcined to obtain the positive electrode active material.
  • the preparation method of the above-mentioned positive electrode active material is simple and has high manufacturability.
  • providing raw materials includes: stirring the sodium source, manganese source, iron source, nickel source, antimony source and L source evenly to obtain the raw materials, wherein the L source is selected from the group consisting of Cu source, Li source, Ti source, Zr source, K source, Nb source, Mg source, Ca source, Mo source, Zn source, Cr source, W source, Bi source, Sn source, Ge source, Al source, Si source, La source , Ta source, P source and B source, one or more.
  • the L source is selected from the group consisting of Cu source, Li source, Ti source, Zr source, K source, Nb source, Mg source, Ca source, Mo source, Zn source, Cr source, W source, Bi source, Sn source, Ge source, Al source, Si source, La source , Ta source, P source and B source, one or more.
  • the sodium source is selected from one or more of Na 2 CO 3 , NaHCO 3 , NaOH and Na 2 O 2 .
  • the iron source is selected from one or more of Fe 2 O 3 , Fe 3 O 4 and FeO.
  • the manganese source is selected from one or more of Mn 2 O 3 , Mn 3 O 4 , MnO and MnO 2 .
  • the nickel source is selected from NiO or Ni(OH) 2 .
  • the antimony source is selected from one or more of elemental antimony, antimony-containing oxides or antimony salts.
  • providing raw materials includes: mixing an iron source, a manganese source, a nickel source, an L source and water to obtain a mixed liquid, wherein the L source is selected from a Cu source, a Li source, and a Ti source.
  • the sodium source is selected from one or more of Na 2 CO 3 , NaHCO 3 , NaOH and Na 2 O 2 .
  • the iron source is selected from one or more of iron-containing chlorides, sulfates and nitrates.
  • the manganese source is selected from one or more of manganese-containing chlorides, sulfates and nitrates.
  • the nickel source is selected from one or more of nickel-containing chlorides, sulfates and nitrates.
  • the antimony source is selected from one or more of elemental antimony, antimony-containing oxides or antimony salts.
  • the precipitating agent is selected from one or more of hydroxide, carbonate and oxalate.
  • the third aspect of the application also provides a secondary battery, including the cathode active material of the first aspect of the application or the cathode active material prepared by the preparation method of the second aspect of the application.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • a sixth aspect of the present application provides an electrical device, including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application. kind.
  • Figure 1 is the X-ray diffraction spectrum of the cathode active material according to an embodiment of the present application before and after being soaked in deionized water for 24 hours;
  • Figure 2 is an X-ray diffraction spectrum of the cathode active material of another embodiment of the present application before and after being soaked in deionized water for 24 hours;
  • Figure 3 is the X-ray diffraction spectrum of the antimony-free cathode active material before and after immersion in deionized water for 24 hours;
  • FIG. 4 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 4 .
  • Figure 6 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 8 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 7 .
  • FIG. 9 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • a first aspect of the present application provides a cathode active material.
  • the cathode active material includes a layered antimony-containing sodium composite oxide.
  • the antimony-containing sodium composite oxide has a chemical formula as shown in Formula I,
  • L is selected from Cu, Li, Ti, Zr, K, Nb, Mg, Ca, Mo, Zn, Cr, W, Bi, Sn, Ge, Al, Si, One or more of La, Ta, P and B.
  • the antimony-containing sodium composite oxide provided by the present application has a specific chemical composition.
  • the antimony-containing sodium composite oxide has a chemical formula as shown in formula I, Na x Mn a Fe b Ni c Sb d L e O 2 (I) .
  • doping with the specific metal Sb can make the layered antimony-containing sodium composite oxide highly stable to water, and can effectively inhibit the antimony-containing sodium in the electrochemical reaction.
  • the by-products formed by undesired chemical reactions on the particle surface of the composite oxide enable the antimony-containing sodium composite oxide to have high cycle stability and to stably exert its electrochemical performance.
  • the inventor has discovered through research that when a layered sodium composite oxide containing Ni and/or Fe (without Sb) is in contact with water, sodium ions in the layered sodium composite oxide will exchange with hydrogen ions, and the hydrogen ions will be embedded in the layer. between the like structures, causing the layered structure to collapse and destroy, and Ni and/or Fe will react with water to generate NiO and/or Fe m On (such as FeO, Fe 2 O 3 , Fe 3 O 4 ), affecting the layered structure stability. Moreover, during the electrochemical process of the layered sodium composite oxide, it will react with the electrolyte to generate by-products such as NiO and/or Fe m O n on the particle surface of the layered sodium composite oxide.
  • the layered sodium composite oxide The electrochemical performance of the material is greatly reduced.
  • the inventor also reduced the content of Ni and/or Fe in the layered sodium composite oxide to suppress the occurrence of by-products such as NiO and/or Fe 3 O 4.
  • the content of Ni and/or Fe decreased, the The specific capacity of sodium-ion batteries formed with layered sodium composite oxide as the positive electrode active material also decreased during the first charge and discharge.
  • the antimony-containing sodium composite oxide doped with a specific element Sb of the present application can significantly improve the performance of the cathode active material containing Ni and/or Fe without reducing the first charge-discharge specific capacity. water stability.
  • the inventor believes that the reasons why doping a certain amount of Sb can achieve the above effect are as follows. Specifically, when a layered sodium composite oxide containing Ni and/or Fe without Sb is in contact with water, the sodium ions between the layers will be exchanged with hydrogen ions, and the hydrogen ions will be embedded in the layered structure.
  • the atomic radius is significantly smaller than that of sodium ions, which reduces the interlayer spacing and even causes the layered structure to collapse and be destroyed.
  • Sb When a certain amount of Sb is doped into such a layered sodium composite oxide, part of Ni and/or Fe in the layered structure crystal is replaced by Sb.
  • Sb since Sb has a strong interaction with Na and can even be alloyed, when the Sb-doped layered sodium composite oxide comes into contact with water, the degree of exchange of sodium ions and hydrogen ions between the layers is reduced.
  • Sb has higher chemical stability, it is not easy to react with water to form oxides and destroy the layered crystal structure.
  • the Sb-doped layered sodium composite oxide can effectively suppress side reactions with the electrolyte, making the antimony-containing sodium composite oxide have high cycle stability. properties and the ability to stably exert its electrochemical properties.
  • Mn, Sb and L are doped in the antimony-containing sodium composite oxide, wherein L is selected from Cu, Li, Ti, Zr, K, Nb, Mg, Ca, Mo, Zn , one or more of Cr, W, Bi, Sn, Ge, Al, Si, La, Ta, P and B, which can further enhance the stability of the layered antimony-containing sodium composite oxide to water, and Cycling stability of antimony-containing sodium complex oxides in electrochemical processes.
  • x is 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85 , 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99 or 1 in other ranges composed of any two of the above endpoints.
  • 0 ⁇ d ⁇ 0.1 in Formula I is used to control the content of doped Sb to be relatively low to avoid excessive Sb doping, resulting in the inclusion of the antimony-containing sodium composite oxide of the present application.
  • Sodium-ion batteries have reduced first charge-discharge specific capacity.
  • formula I (b+c)/(a+d+e) ⁇ 1 in order to control the appropriate content of doped Fe and/or Ni, it is possible to prevent excessive Fe and /or Ni is more likely to react with water, and can also prevent Fe and/or Ni in the antimony-containing sodium composite oxide from reacting with the electrolyte during the electrochemical process, thereby effectively suppressing the occurrence of side reactions.
  • formula I (b+c)/(a+d+e) ⁇ 1 it means that the total doping content of Sb, Mn and L is greater than or equal to the total doping content of Fe and Ni, thus ensuring that antimony-containing sodium Structural stability of complex oxides.
  • doping with specific metal Sb can make the layered antimony-containing sodium composite oxide have higher stability to water.
  • Sb and O have strong covalent interactions, which can at least improve the stability of the layered antimony-containing sodium composite oxide.
  • the local structural stability of the sodium composite oxide inhibits side reactions such as proton exchange that occur when the layered antimony-containing sodium composite oxide contacts water molecules, thereby increasing its water stability.
  • the side reactions of the antimony-containing sodium composite oxide can be effectively suppressed, so that the antimony-containing sodium composite oxide has high cycle stability and can stably exert its electrochemical performance. .
  • a is 0.4, b is 0.2, c is 0.2, d is 0.1, and e is 0.1.
  • the antimony-containing sodium composite oxide in which the ratio of each element meets the above requirements can improve the orderliness of the cations in the layered structure, ensuring that the cathode active material has higher structural stability. properties, thereby making the positive active material more stable to water.
  • the antimony-containing sodium composite oxide may contain higher contents of Fe and Ni, so that a sodium ion battery using such a cathode active material has a higher first charge-discharge specific capacity. . Therefore, the antimony-containing sodium composite oxide according to this embodiment better balances stability against water, cycle stability in the electrochemical process, and first charge-discharge specific capacity.
  • L is selected from one or more of Cu, Li, Ti, Zr, Mg, Ca, Zn, Bi, Sn, Al, Si, La, Ta, P and B.
  • L is selected from one or more of Cu, Li, Mg, Zn, Al, Si and B.
  • These specific optional additional doping elements can enhance the stability of the layered antimony-containing sodium composite oxide to water, as well as the cycle stability of the antimony-containing sodium composite oxide in the electrochemical process.
  • these specific optional examples of L have good stability to the electrolyte and are also beneficial to the wetting of the electrolyte.
  • the layered antimony-containing sodium composite oxide of the present application is used as a positive electrode active material. According to the stable phase structure of the layered antimony-containing sodium composite oxide, it can be classified into layered metal oxides such as P2 phase and O3 phase.
  • the antimony-containing sodium composite oxide includes an O3 phase, the O3 phase having a space group layered crystal structure.
  • O3 has greater advantages than other phases in both specific capacity and specific energy.
  • the antimony-containing sodium composite oxide of the present application includes an O3 phase, and the O3 phase has a space group
  • the layered crystal structure of the cathode active material with this crystal structure has good structural stability and is conducive to improving the capacity performance and cycle performance of the cathode active material.
  • the antimony-containing sodium composite oxide has a layer spacing of 0.53 nm to 0.54 nm.
  • the interlayer spacing of the antimony-containing sodium composite oxide is 0.534 nm to 0.548 nm.
  • the interlayer spacing (d 003 ) of the antimony-containing sodium composite oxide when the interlayer spacing (d 003 ) of the antimony-containing sodium composite oxide is controlled within this range, the structure of the cathode active material is more stable, which shows that the cycle performance of the cathode active material is better. At the same time, sodium ions are more easily deintercalated between layers, which can better improve the charge-discharge specific capacity of the cathode active material.
  • the interlayer spacing of the antimony-containing sodium composite oxide is between 0.53nm and 0.54nm, which is beneficial to the conduction and diffusion of sodium ions between layers, and can also inhibit the interaction of hydrogen ions with the layered antimony-containing sodium composite oxide when it encounters water. The exchange reaction of sodium ions occurs, making the antimony-containing sodium composite oxide more stable to water.
  • the X-ray diffraction spectrum of the antimony-containing sodium composite oxide satisfies I 1 /I 0 ⁇ 0.2
  • I 1 is the peak intensity of the X-ray diffraction peak of the O3 phase 003 crystal plane of the antimony-containing sodium composite oxide after soaking in deionized water for 24 hours
  • I 0 is the antimony-containing sodium that has not been soaked in deionized water.
  • the X-ray diffraction spectrum of the antimony-containing sodium composite oxide satisfies 0.2 ⁇ I 1 /I 0 ⁇ 1, and I 1 /I 0 reflects the response of the antimony-containing sodium composite oxide to water in the O3 phase layer. degree of sensitivity.
  • the X-ray diffraction spectrum of the antimony-containing sodium composite oxide satisfies 0.35 ⁇ I 1 /I 0 ⁇ 1.
  • the X-ray diffraction spectrum of the antimony-containing sodium composite oxide satisfies 0.6 ⁇ I 1 /I 0 ⁇ 0.9.
  • Figure 1 is an X-ray diffraction spectrum of a positive electrode active material according to one embodiment of the present application before and after being soaked in deionized water for 24 hours
  • Figure 2 is an X-ray diffraction spectrum of a positive electrode active material according to another embodiment of the present application before and after being soaked in deionized water for 24 hours.
  • Figure 3 is the X-ray diffraction spectrum of the antimony-free cathode active material before and after immersion in deionized water for 24 hours.
  • Figure 1 shows the X-ray diffraction spectra of antimony-containing sodium composite oxide NaNi 0.2 Fe 0 . 29 Mn 0.4 Cu 0.1 Sb 0.01 O 2 before and after immersion in deionized water for 24 hours.
  • the solid line part in Figure 1 is the X-ray diffraction pattern of the O3 phase of the antimony-containing sodium composite oxide that has not been soaked in deionized water (before soaking), and the dotted line part is the antimony-containing sodium composite oxide after deionization.
  • I 1 /I 0 is 0.35, and the positions of the characteristic peaks in the two X-ray diffraction patterns are basically the same, indicating that the antimony-containing sodium composite oxide NaNi 0.2 Fe 0 . 29 Mn 0.4 Cu 0.1 Sb 0.01
  • the crystal structure of O2 did not change substantially after being soaked in deionized water for 24 hours. Therefore, the antimony-containing sodium composite oxide is not sensitive to water, which can be understood as its strong stability to water.
  • Figure 2 shows the X-ray diffraction spectra of antimony-containing sodium composite oxide NaNi 0.2 Fe 0.2 Mn 0.4 Cu 0.1 Sb 0.1 O 2 before and after immersion in deionized water for 24 hours.
  • the solid line part in Figure 2 is the X-ray diffraction pattern of the O3 phase of the antimony-containing sodium composite oxide that has not been soaked in deionized water (before soaking), and the dotted line part is the antimony-containing sodium composite oxide after deionization.
  • I 1 /I 0 is 0.86, and the positions of the characteristic peaks in the two X-ray diffraction patterns are basically the same, indicating that the antimony-containing sodium composite oxide NaNi 0.2 Fe 0.2 Mn 0.4 Cu 0.1 Sb 0.1 O 2. Its crystal structure does not change substantially after being soaked in deionized water for 24 hours. Therefore, the antimony-containing sodium composite oxide is not sensitive to water and is more stable to water.
  • Figure 3 shows the X-ray diffraction spectra of antimony-free sodium composite oxide NaNi 0.2 Fe 0.29 Mn 0.4 Cu 0.11 O 2 before and after immersion in deionized water for 24 hours.
  • the solid line in Figure 3 is the X-ray diffraction pattern of the O3 phase crystal of the sodium composite oxide that has not been soaked in deionized water (before soaking), and the dotted line is the sodium composite oxide after soaking in deionized water for 24 hours.
  • X-ray diffraction pattern (after soaking).
  • I 1 /I 0 is 0.08, and the positions of the characteristic peaks in the two X-ray diffraction patterns deviate, indicating that the antimony-free sodium composite oxide is immersed in deionized water for 24 hours.
  • the crystal structure changes significantly, so the antimony-free sodium composite oxide is more sensitive to water and has poor stability to water.
  • doping with antimony enhances the interaction between transition metals and oxygen in the O3 phase layered antimony-containing sodium composite oxide, thereby increasing the stability to water, which is reflected in I In terms of the 1 /I 0 parameter, the greater the ratio of I 1 /I 0 , the less sensitive it is to water, indicating that the antimony-containing sodium composite oxide is more stable to water.
  • the volume average particle size Dv50 of the positive active material is 3 ⁇ m to 30 ⁇ m.
  • the volume average particle size Dv50 of the positive electrode active material is 5 ⁇ m to 15 ⁇ m.
  • the volume average particle size Dv50 of the positive electrode active material can be measured using conventional methods in the art.
  • the volume average particle size Dv50 of the cathode active material is within an appropriate range, which is conducive to obtaining a higher compaction density of the cathode active material layer and at the same time having appropriate porosity to satisfy the electrochemical reaction.
  • the required amount of electrolyte infiltration also has a shorter migration path for active ions and electrons within the particles, which can improve the energy density and cycle performance of the cathode active material layer.
  • the cathode active material has a specific surface area of 0.1 m 2 /g to 5 m 2 /g.
  • the specific surface area of the positive active material is 0.3 m 2 /g ⁇ 3 m 2 /g.
  • the specific surface area of the positive active material has a meaning known in the art and can be measured using instruments and methods known in the art.
  • BET Brunauer Emmett Teller
  • the cathode active material has an appropriate specific surface area, which can reduce the liquid absorption phenomenon during the preparation process of the cathode slurry, improve the solid content and particle dispersion uniformity in the cathode slurry, and thereby improve the content of the cathode slurry.
  • the particle dispersion uniformity and compaction density in the film layer of the positive electrode active material can thereby increase the specific capacity and energy density of the sodium-ion battery, and improve the cycle performance of the sodium-ion battery.
  • the positive active material has a tap density of 1 to 3 g/cm 3 .
  • the tap density of the positive active material is 1.5g/cm 3 to 2.5g/cm 3 .
  • the tap density of the positive active material has a meaning known in the art and can be measured using instruments and methods known in the art.
  • the tap density can be measured with reference to GB/T5162-2006 Powder Tap Density Determination Method. It can be carried out with an instrument, such as FZS4-4B tap density measuring instrument.
  • the positive electrode active material has an appropriate tap density, which is beneficial to the positive electrode active material having a higher compacted density, so that the sodium ion battery has higher capacity performance and energy density.
  • the powder compaction density of the cathode active material under a pressure of 8 tons is 3g/cm 3 to 5g/cm 3 , optionally 3.5g/cm 3 to 4.5g/cm 3 .
  • the compacted density of the positive active material has a meaning well known in the art, and can be measured using instruments and methods known in the art. For example, it can be measured with reference to the GB/T24533-2009 standard and through an electronic pressure testing machine, such as UTM7305. Electronic pressure testing machine.
  • the positive active material has a higher compacted density, which is beneficial to the sodium-ion battery having higher capacity performance and energy density.
  • the higher the compacted density of the positive active material the higher the capacity performance and energy density of the sodium-ion battery will be.
  • Preparation method of positive electrode active material including:
  • the raw materials are calcined to obtain the positive active material.
  • the positive active material includes a layered antimony-containing sodium composite oxide, and the antimony-containing sodium composite oxide has a chemical formula as shown in formula I,
  • L is selected from Cu, Li, Ti, Zr, K, Nb, Mg, Ca, Mo, Zn, Cr, W, Bi, Sn, Ge, Al, Si, One or more of La, Ta, P and B.
  • the raw materials of the cathode active material can be prepared by a co-precipitation method, a gel method or a solid phase method.
  • the positive electrode active material preparation method of the present application raw materials are first provided, and then the raw materials are calcined to obtain the positive electrode active material.
  • the preparation method of the above-mentioned positive electrode active material is simple and has high manufacturability.
  • step S1 of providing raw materials includes: stirring the sodium source, manganese source, iron source, nickel source, antimony source and L source evenly to obtain the raw materials.
  • a ball mill mixer or a high-speed mixer can be used for mixing.
  • the sodium source, manganese source, iron source, nickel source, antimony source and L source are added to a high-speed mixer according to the stoichiometric ratio for mixing, and the mixing time is 0.5h to 2h.
  • a sodium source, a manganese source, an iron source, a nickel source, an antimony source and an L source are mixed to obtain a raw material.
  • the L source is selected from the group consisting of Cu source, Li source, Ti source, Zr source, K source, Nb source, Mg source, Ca source, Mo source, Zn source, Cr source, W source, and Bi source. , one or more of Sn source, Ge source, Al source, Si source, La source, Ta source, P source and B source.
  • the sodium source is selected from one or more of Na 2 CO 3 , NaHCO 3 , NaOH and Na 2 O 2 .
  • the iron source is selected from one or more of Fe 2 O 3 , Fe 3 O 4 and FeO.
  • the manganese source is selected from one or more of Mn 2 O 3 , Mn 3 O 4 , MnO and MnO 2 .
  • the nickel source is selected from NiO or Ni(OH) 2 .
  • the antimony source is selected from one or more of elemental antimony, antimony-containing oxides or antimony salts.
  • step S1 provides raw materials including: mixing iron source, manganese source, nickel source, L source and water to obtain a mixed liquid; mixing the mixed liquid with a precipitant to form a precipitate; mixing the precipitate, sodium Stir the source and antimony source evenly to obtain raw materials.
  • the manganese source, iron source, nickel source and L source are precipitated, and then mixed with the sodium source and antimony source through a ball mill mixer or a high-speed mixer to obtain raw materials.
  • the L source is selected from the group consisting of Cu source, Li source, Ti source, Zr source, K source, Nb source, Mg source, Ca source, Mo source, Zn source, Cr source, W source, and Bi source. , one or more of Sn source, Ge source, Al source, Si source, La source, Ta source, P source and B source;
  • the sodium source is selected from one or more of Na 2 CO 3 , NaHCO 3 , NaOH and Na 2 O 2 .
  • the iron source is selected from one or more of iron-containing chlorides, sulfates and nitrates.
  • the manganese source is selected from one or more of manganese-containing chlorides, sulfates and nitrates.
  • the nickel source is selected from one or more of nickel-containing chlorides, sulfates, and nitrates.
  • the antimony source is selected from one or more of elemental antimony, antimony-containing oxides or antimony salts.
  • the precipitating agent is selected from one or more of hydroxide, carbonate and oxalate.
  • the calcination in step S2 includes calcining the raw materials in a muffle furnace, the calcination temperature is 600°C to 1200°C, the atmosphere is air or oxygen atmosphere, and the holding time is 10h to 20h.
  • the calcination temperature has a greater impact on the performance of the cathode active material.
  • the calcination temperature is low, the reaction is incomplete and amorphous materials are easily generated and contain impurity phases, which have a greater impact on the electrochemical performance of the cathode active material.
  • the diffusion coefficient of the material increases, which promotes the diffusion of ions and vacancies, particle rearrangement and other material transfer processes, which is beneficial to obtaining products with high structural stability.
  • oxygen-deficient compounds are easily generated, which is not conducive to the extraction and insertion of sodium ions in the cathode active material.
  • the calcination temperature is 900°C to 950°C, and the holding time is 15h to 20h.
  • pre-calcination can be carried out before calcination as needed.
  • the temperature of pre-calcination is 600°C to 900°C
  • the atmosphere is air or oxygen atmosphere
  • the holding time is 10h to 20h.
  • the calcination in step S2 also includes mechanical pulverization after cooling to obtain the cathode active material.
  • the volume average particle diameter Dv50 of the positive electrode active material is 3 ⁇ m to 30 ⁇ m. It is beneficial to make the finally obtained cathode active material have better particle size distribution and specific surface area.
  • FIG. 4 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 4 .
  • Figure 6 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 8 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 7 .
  • FIG. 9 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • a third aspect of the application provides a secondary battery, including the cathode active material of the first aspect of the application or the cathode active material prepared by the preparation method of the second aspect of the application.
  • a secondary battery typically includes a positive electrode plate, a negative electrode plate, an electrolyte and a separator.
  • active ions are inserted and detached back and forth between the positive and negative electrodes.
  • the electrolyte plays a role in conducting ions between the positive electrode piece and the negative electrode piece.
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer formed on at least part of the surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material, and the positive electrode active material is the positive electrode active material of the first aspect of the present application.
  • the cathode active material prepared by the preparation method of the second aspect of the present application is also applicable to the cathode active material in the secondary battery, and the same content will not be described again.
  • the positive electrode film layer may further include a conductive agent to improve the conductive performance of the positive electrode.
  • a conductive agent to improve the conductive performance of the positive electrode.
  • the conductive agent can be one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene and carbon nanofibers.
  • the positive electrode film layer may further include a binder to firmly bond the positive electrode active material and optional conductive agent to the positive electrode current collector.
  • a binder to firmly bond the positive electrode active material and optional conductive agent to the positive electrode current collector.
  • the binder may be polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVA), styrene-butadiene At least one of rubber (SBR), carboxymethyl cellulose (CMC), sodium alginate (SA), polymethacrylic acid (PMA) and carboxymethyl chitosan (CMCS).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • EVA ethylene-vinyl acetate copolymer
  • SBR carboxymethyl
  • the positive electrode current collector can be a conductive carbon sheet, metal foil, carbon-coated metal foil, porous metal plate or composite current collector, wherein the conductive carbon material of the conductive carbon sheet can be superconducting carbon, acetylene black, carbon One or more of black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene and carbon nanofibers, the metal materials of metal foil, carbon-coated metal foil and porous metal plate can be independently selected from At least one of copper, aluminum, nickel and stainless steel.
  • the composite current collector may be a composite current collector formed by a combination of a metal foil material and a polymer base film.
  • the positive electrode current collector is, for example, one or more of copper foil, aluminum foil, nickel foil, stainless steel foil, stainless steel mesh, and carbon-coated aluminum foil. Aluminum foil is preferably used.
  • the above-mentioned positive electrode sheet can be prepared according to conventional methods in the art.
  • the positive electrode active material and optional conductive agent and binder are dispersed in a solvent (such as N-methylpyrrolidone, referred to as NMP) to form a uniform positive electrode slurry, and the positive electrode slurry is coated on the positive electrode current collector , after drying and cold pressing, the positive electrode piece is obtained.
  • a solvent such as N-methylpyrrolidone, referred to as NMP
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, where the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative electrode film layer optionally further includes a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polysodium acrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • auxiliaries such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays a role in conducting ions between the positive electrode piece and the negative electrode piece.
  • the type of electrolyte in this application can be selected according to needs.
  • the electrolyte can be liquid, gel, or completely solid.
  • the electrolyte is an electrolyte solution.
  • the electrolyte solution includes electrolyte salts and solvents.
  • the electrolyte salt may be NaPF 6 , NaClO 4 , NaBF 4 , KPF 6 , KClO 4 , KBF 4 , LiPF 6 , LiClO 4 , LiBF 4 , Zn(PF 6 ) 2 , Zn(ClO 4 ) 2 , one or more of Zn(BF 4 ) 2 .
  • the electrolyte salt can be selected from one or more of NaPF 6 , NaClO 4 , and NaBF 4 .
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte optionally further includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • isolation membrane there is no particular restriction on the type of isolation membrane, and any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece, and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 4 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 6 shows a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and 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 also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • FIG. 9 shows an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • the device is usually required to be thin and light, and a secondary battery can be used as a power source.
  • the raw materials are evenly placed in an open crucible, and then heated from room temperature to 950°C at a heating rate of 5°C/min in a muffle furnace, and kept at a constant temperature of 950°C for 15 hours, followed by natural cooling to obtain a positive active material, where,
  • the positive active material is layered NaNi 0.2 Mn 0.5 Cu 0.2 Sb 0.1 O 2 .
  • the cathode active materials of Examples 1 to 19 and Comparative Examples 1 to 6 were prepared according to Table 1 below.
  • the above-mentioned positive electrode active material, conductive carbon black (SP), and binder polyvinylidene fluoride (PVDF) are fully stirred and mixed in an appropriate amount of N-methylpyrrolidone (NMP) solvent at a weight ratio of 80:15:5. It forms a uniform positive electrode slurry; this slurry is coated on the carbon-coated Al foil of the positive electrode current collector, dried, cold-pressed and punched into small discs with a diameter of 14 mm.
  • NMP N-methylpyrrolidone
  • the negative electrode piece is made of metal sodium piece.
  • the isolation membrane uses porous polyethylene film.
  • Electrode assembly Stack the positive electrode piece, the isolation film, and the negative electrode piece in order and wind them to obtain an electrode assembly.
  • the electrode assembly is placed in the outer packaging, the electrolyte prepared above is added, and after processes such as packaging, standing, formation, and aging, a secondary battery is obtained.
  • the sample preparation After the sample preparation is completed, use the Brucker D8A_A25 X-ray powder diffractometer from Brucker AxS Company in Germany, using CuK ⁇ rays as the radiation source, and the ray wavelength
  • the scanning 2 ⁇ angle range is 10° to 70°, and the scanning rate is 4°/min for testing.
  • the space group of the sample can be confirmed.
  • I 1 represents the intensity of the characteristic peak (003) in the X-ray diffraction spectrum of the positive electrode active material after being soaked in water for 24 hours
  • I 0 represents the intensity of the characteristic peak (003) in the X-ray diffraction spectrum of the positive electrode active material before soaking in water
  • I 1 /I 0 can represent the water stability of the cathode active material. The smaller I 1 /I 0 is, the worse the water stability of the cathode active material is and the more sensitive it is to water.
  • the cathode active material prepared in the above example was placed in an air environment with a humidity of 70% and a temperature of 25°C for one day, and the above-mentioned cathode active material was placed under conventional storage conditions for one day (humidity ⁇ 1%, temperature 25°C).
  • the two kinds of The cathode active materials under storage conditions were made into batteries respectively, and their capacities were tested, and the high-humidity storage capacity change rate of the cathode active materials was calculated.
  • the positive active material into a secondary battery, charge it to 4.3V with a constant current density of 10mA/g, and then discharge it to 1.5V with a constant current density of 10mA/g to obtain a secondary battery.
  • the discharge specific capacity of the battery C 0 The same positive active material was left in the air for one day at a humidity of 70% and a temperature of 25°C.
  • Examples 1 to 19 have all achieved good results, with moderate layer spacing, large I 1 /I 0 value, and the specific surface area of the positive active material is, tap density and powder under 8 tons of pressure.
  • the bulk compacted density is high, and the capacity change rate of high-humidity storage is high. The higher the change rate, the better the stability to water.
  • the layered antimony-containing sodium composite oxide can be made highly stable to water, and can effectively inhibit the antimony-containing sodium composite oxide during the electrochemical reaction.
  • a side reaction occurs, thereby obtaining a higher specific surface area, tap density and powder compaction density under a pressure of 8 tons, thereby increasing the specific capacity of the first charge and discharge of the sodium ion battery containing the cathode active material of the present application. higher.
  • Comparative Example 1 does not include the antimony-doped cathode active material.
  • the I 1 /I 0 value of the cathode active material is small, indicating that the cathode active material has poor water stability.
  • the content of doped Fe and Ni is too high. Excessive Fe and Ni are more likely to react with water, making the I 1 /I 0 value of the cathode active material small, indicating that the cathode active material is sensitive to water. Poor stability.
  • the cathode active material contains lower contents of Fe and Ni, so that the sodium ion battery using such cathode active material has a lower first charge-discharge specific capacity, and also reduces the interlayer structure of the layered antimony-containing sodium composite oxide. stability. Comparative Examples 5 and 6 show that excessive doping of Sb is avoided, resulting in a reduced first charge-discharge specific capacity of the sodium-ion battery, and too little doping of Sb cannot satisfy the stability of the cathode material towards water.

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Abstract

本申请实施例提供一种正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置。本申请的正极活性材料，包括层状的含锑的钠复合氧化物，所述含锑的钠复合氧化物具有如式I所示的化学式，Na xMn aFe bNi cSb dL eO 2(I)在所述式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d≤0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。根据本申请的通过掺杂有特定金属Sb能够使得层状含锑的钠复合氧化物对水具有较高稳定性。。

Description

正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置 技术领域
本申请涉及电池技术领域，特别是涉及一种正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置。
背景技术
近年来，随着锂离子电池的应用范围越来越广泛，锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。随着锂离子电池制造所需资源的紧缺和Ni、Co等原材料的成本升高，寻找成本低廉的锂离子电池替代物，已经成为新能源领域的研究热点。
钠离子电池具有储量丰富、成本低廉、体系安全，低温和高倍率等优势，是锂离子电池的优良继承者。但是，现有的钠离子电池正极活性材料的水稳定性较差、比容量较低，限制了钠离子电池的发展。
发明内容
本申请是鉴于上述课题而进行的，提供一种正极活性材料及其制备方法、二次电池、电池模块、电池包和用电装置，用于解决钠离子电池正极活性材料的水稳定性较差、比容量较低的问题。
为了达到上述目的，本申请的第一方面提供了一种正极活性材料，包括层状的含锑的钠复合氧化物，含锑的钠复合氧化物具有如式I所示的化学式，
Na xMn aFe bNi cSb dL eO 2   (I)
在式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d≤0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
根据本申请的通过掺杂有特定金属Sb能够使得层状含锑的钠复合氧化物对水具有较高稳定性，并且，在电化学反应过程中，能够有效地抑制含锑的钠复合氧化物发生副反应，使得含锑的钠复合氧化物具有较高的循环稳定性，以及能够稳定地发挥其电化学性能，从而提高钠离子电池的首次充放电的比容量。
在本申请第一方面的任一实施方式中，在式I中，0.3≤a≤0.4，0.2≤b≤0.3，0.15≤c≤0.2，0.05≤d≤0.1，0.05≤e≤0.1，a+b+c+d+e＝1，0.4≤(b+c)/(a+d+e)≤1。
在这些可选的实施例中，含锑的钠复合氧化物中各元素的配比满足上述要求，能够提高层状结构中阳离子的排列有序程度，保证了正极活性材料具有较高的结构稳定性，从而使得正极活性材料对水稳定性更强。另一方面，根据这些可选的实施例，含锑的钠复合氧化物可以包含较高含量的Fe和Ni，以使得使用这样的含锑的钠复合氧化物正极活性材料的钠离子电池具有更高的首次充放电比容量。因此，根据本实施例的含锑的钠复合氧化物更好地兼顾了对水稳定性、电化学过程中的循环稳定性以及首次充放电比容量。
在本申请第一方面的任一实施方式中，L选自Cu、Li、Ti、Zr、Mg、Ca、Zn、Bi、Sn、Al、Si、La、Ta、P和B中的一种或几种，可选地，L选自Cu、Li、Mg、Zn、Al、Si和B中的一种或几种。
这些具体可选附加掺杂元素能够增强层状的含锑的钠复合氧化物对水的稳定性，以及含锑的钠复合氧化物在电化学过程中的循环稳定性。而且，这些具体可选的L示例对电解液的稳定性好，还有利于电解液的浸润。
在本申请第一方面的任一实施方式中，含锑的钠复合氧化物包括O3相，O3相为具有空间群
Figure PCTCN2022105646-appb-000001
的层状晶体结构。
在这些可选的实施例中，O3相比于其他相在比容量和比能量两方面都具有较大的优势。本申请含锑的钠复合氧化物包括O3相，O3相为具有空间群
Figure PCTCN2022105646-appb-000002
的层状晶体结构，具有该种晶体结构的正极活性材料，其结构稳定性好，有利于提高正极活性材料的容量性能及循环性能。
在本申请第一方面的任一实施方式中，含锑的钠复合氧化物的层间距为0.53nm～0.54nm。
在这些可选的实施例中，含锑的钠复合氧化物的层间距(d 003)控制在此范 围内时，正极活性材料的结构更加稳定，表现为正极活性材料的循环性能更好。同时钠离子在层间更容易脱嵌，更好地提高正极活性材料的充放电比容量。此外，含锑的钠复合氧化物的层间距在0.53nm～0.54nm之间，有利于钠离子在层间的传导扩散，又能抑制层状含锑的钠复合氧化物遇水时氢离子与钠离子发生交换，从而使得含锑的钠复合氧化物对水具有更高的稳定性。
在本申请第一方面的任一实施方式中，含锑的钠复合氧化物的X射线衍射谱满足I 1/I 0≥0.2，
其中，I 1为在去离子水浸泡24h后的含锑的钠复合氧化物的O3相003晶面的X射线衍射峰的峰强度，I 0为未在去离子水内浸泡的含锑的钠复合氧化物的O3相003晶面的X射线衍射峰的峰强度。
在这些可选的实施例中，采用锑进行掺杂增强了O3相层状含锑的钠复合氧化物中过渡金属和氧的相互作用力，从而增加了对水的稳定性，这体现在I 1/I 0参数上，I 1/I 0的比值越大，说明对水越不敏感，以表明含锑的钠复合氧化物对水的稳定性越强。
在本申请第一方面的任一实施方式中，正极活性材料的体积平均粒径Dv50为3μm～30μm，可选为5μm～15μm。
在这些可选的实施例中，正极活性材料的体积平均粒径Dv50在适当范围内，有利于使正极活性材料层获得较高的压实密度，同时具有合适的孔隙率，来满足电化学反应所需的电解液浸润量，还具有较短的颗粒内活性离子和电子的迁移路径，由此能够提高正极活性材料层的能量密度和循环性能。
在本申请第一方面的任一实施方式中，正极活性材料的比表面积为0.1m 2/g～5m 2/g，可选为0.3m 2/g～3m 2/g。
在这些可选的实施例中，正极活性材料具有适当的比表面积，能够减少正极浆料制备过程中的吸液现象，提高正极浆料中的固含量及颗粒分散均匀性，从而能够提高包含正极活性材料的膜层中颗粒分散均匀性和压实密度，进而提高了钠离子电池的比容量和能量密度，并改善钠离子电池的循环性能。
在本申请第一方面的任一实施方式中，正极活性材料的振实密度为1g/cm 3～3g/cm 3，可选为1.5g/cm 3～2.5g/cm 3。
在这些可选的实施例中，正极活性材料具有适当的振实密度，有利于使正 极活性材料具有较高的压实密度，从而使得钠离子电池具有较高的容量性能及能量密度。
在本申请第一方面的任一实施方式中，正极活性材料在8吨压力下的粉体压实密度为3g/cm 3～5g/cm 3，可选地为3.5g/cm 3～4.5g/cm 3。
在这些可选的实施例中，正极活性材料具有较高的压实密度，有利于使钠离子电池具有较高的容量性能及能量密度。在此范围内，正极活性材料的压实密度越高，钠离子电池的容量性能及能量密度相应地越高。
申请的第二方面还提供一种正极活性材料的制备方法，包括：
提供原料，使得原料中的元素配比满足本申请第一方面的式I所示的化学式；
将原料进行煅烧处理，得到正极活性材料，
其中，正极活性材料包括层状的含锑的钠复合氧化物，含锑的钠复合氧化物具有如式I所示的化学式，
Na xMn aFe bNi cSb dL eO 2   (I)
在式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d＜0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
根据本申请的正极活性材料制备方法的实施例，先提供原料，再将原料煅烧，得到正极活性材料。上述正极活性材料的制备方法简单，且可制造性高。
在本申请第二方面的任一实施方式中，提供原料包括：将钠源、锰源、铁源、镍源、锑源和L源搅拌均匀，获得原料，其中，L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种。
在本申请第二方面的任一实施方式中，钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种。
在本申请第二方面的任一实施方式中，铁源选自Fe 2O 3、Fe 3O 4和FeO中的一种或几种。
在本申请第二方面的任一实施方式中，锰源选自Mn 2O 3、Mn 3O 4、MnO和MnO 2中的一种或几种。
在本申请第二方面的任一实施方式中，镍源选自NiO或Ni(OH) 2。
在本申请第二方面的任一实施方式中，锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种。
在本申请第二方面的任一实施方式中，提供原料包括：将铁源、锰源、镍源、L源与水混合，获得混合液，其中，L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种；将混合液与沉淀剂混合，形成沉淀物；将沉淀物、钠源和锑源搅拌均匀，获得原料。
在本申请第二方面的任一实施方式中，钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种。
在本申请第二方面的任一实施方式中，铁源选自含铁的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请第二方面的任一实施方式中，锰源选自含锰的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请第二方面的任一实施方式中，镍源选自含镍的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请第二方面的任一实施方式中，锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种。
在本申请第二方面的任一实施方式中，沉淀剂选自氢氧化物、碳酸盐和草酸盐中的一种或几种。
申请的第三方面还提供一种二次电池，包括本申请第一方面的正极活性材料或本申请第二方面的制备方法制得的正极活性材料。
本申请的第四方面提供一种电池模块，包括本申请的第三方面的二次电池。
本申请的第五方面提供一种电池包，包括本申请的第四方面的电池模块。
本申请的第六方面提供一种用电装置，包括选自本申请的第三方面的二次电池、本申请的第四方面的电池模块或本申请的第五方面的电池包中的至少一种。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1是本申请一实施方式的正极活性材料在去离子水浸泡24h前后的X射线衍射谱；
图2是本申请另一实施方式的正极活性材料在去离子水浸泡24h前后的X射线衍射谱；
图3是不含锑的正极活性材料在去离子水浸泡24h前后的X射线衍射谱；
图4是本申请一实施方式的二次电池的示意图。
图5是图4所示的本申请一实施方式的二次电池的分解图。
图6是本申请一实施方式的电池模块的示意图。
图7是本申请一实施方式的电池包的示意图。
图8是图7所示的本申请一实施方式的电池包的分解图。
图9是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53盖板。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的用于二次电池的粘结剂、负极极片、二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120 和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
正极活性材料
本申请的第一方面提供了一种正极活性材料，正极活性材料包括层状的含锑的钠复合氧化物，含锑的钠复合氧化物具有如式I所示的化学式，
Na xMn aFe bNi cSb dL eO 2   (I)
在式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d≤0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、 Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
本申请提供的含锑的钠复合氧化物具有特定的化学组成，含锑的钠复合氧化物具有如式I所示的化学式，Na xMn aFe bNi cSb dL eO 2(I)。在本申请的正极活性材料中，掺杂有特定金属Sb能够使得层状含锑的钠复合氧化物对水具有较高稳定性，并且，在电化学反应中，能够有效地抑制含锑的钠复合氧化物的颗粒表面发生不期望的化学反应而形成的副产物，使得含锑的钠复合氧化物具有较高的循环稳定性，以及能够稳定地发挥其电化学性能。
并非希望受限于任何理论，下面进一步解释说明根据本申请实施例的含锑的钠复合氧化物结构稳定性的原因，以更好地理解本申请的目的和有意效果。
发明人经研究发现，在包含Ni和/或Fe的层状钠复合氧化物(不含有Sb)与水接触时，层状钠复合氧化物中钠离子会与氢离子发生交换，氢离子嵌入层状结构间，使层状结构坍塌破坏，并且Ni和/或Fe会与水发生反应生成NiO和/或Fe mO n(例如FeO、Fe 2O 3、Fe 3O 4)，影响层状结构的稳定性。而且，层状钠复合氧化物在电化学过程中，其会与电解液发生反应，在层状钠复合氧化物的颗粒表面生成NiO和/或Fe mO n等副产物，层状钠复合氧化物的电化学性能大大降低。发明人又通过降低层状钠复合氧化物中Ni和/或Fe的含量，以抑制NiO和/或Fe 3O 4等副产物的发生，但是随着Ni和/或Fe的含量的降低，使得层状钠复合氧化物作为正极活性材料形成的钠离子电池的首次充放电的比容量也下降。
本发明人出人意料地发现，本申请的掺杂有特定元素Sb的含锑的钠复合氧化物可以在不降低首次充放电比容量的同时，大幅提升了包含Ni和/或Fe的正极活性材料对水的稳定性。并非希望受限于任何理论，发明人认为掺杂一定量的Sb而能够实现上述效果的原因如下。具体地，当不掺杂Sb的含Ni和/或Fe的层状钠复合氧化物与水接触时，层间的钠离子会与氢离子发生交换，氢离子嵌入层状结构间，由于氢离子的原子半径明显小于钠离子的原子半径，使得层间距减小，甚至导致层状结构坍塌破坏。当在这样的层状钠复合氧化物中掺杂一定量的Sb时，层状结构晶体中的部分Ni和/或Fe被Sb替换。一方面，由于Sb与Na有较强的相互作用，甚至能够合金化，因此当掺杂Sb的层状钠复合氧化物与水接触时，层间的钠离子与氢离子发生交换的程度降低。另一方面，由于Sb具有更高的化学稳定性，不容易与水发生反应生成氧化物而破坏层状晶体结构。此外，在电化学反应(如电池充放电)过程中，掺杂Sb的层状钠 复合氧化物能够有效地抑制与电解液的副反应，使得含锑的钠复合氧化物具有较高的循环稳定性，以及能够稳定地发挥其电化学性能。
在本申请的一些实施例中，含锑的钠复合氧化物中的Mn、Sb以及L的掺杂，其中L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种，能够进一步增强层状的含锑的钠复合氧化物对水的稳定性，以及含锑的钠复合氧化物在电化学过程中的循环稳定性。
在本申请的一些实施例中，在式I中0.7＜x≤1，x为0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.8、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.9、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99或1在由上述的任意两个端点所组成的其它范围内。
在本申请的一些实施例中，在式I中0＜d≤0.1，以控制掺杂Sb的含量相对较低，以避免Sb掺杂过多，导致包含本申请的含锑的钠复合氧化物的钠离子电池具有降低的首次充放电比容量。
在本申请的一些实施例中，在式I中(b+c)/(a+d+e)≤1，以控制掺杂Fe和/或Ni的适宜的含量，能够防止过多的Fe和/或Ni更容易与水发生反应，还能够防止在电化学过程中，含锑的钠复合氧化物中的Fe和/或Ni与电解液发生反应，从而有效抑制抑制副反应的发生。此外，在式I中(b+c)/(a+d+e)≤1，说明Sb、Mn以及L的总掺杂含量大于等于Fe和Ni的总掺杂含量，从而保证含锑的钠复合氧化物的结构稳定性。
根据本申请的通过掺杂有特定金属Sb能够使得层状含锑的钠复合氧化物对水具有较高稳定性，Sb与O具有较强共价相互作用力，至少能够提高层状含锑的钠复合氧化物的局部结构稳定性，抑制层状含锑的钠复合氧化物接触水分子时发生的质子交换等副反应，增加其水稳定性。并且，在电化学反应过程中，能够有效地的抑制含锑的钠复合氧化物发生副反应，使得含锑的钠复合氧化物具有较高的循环稳定性，以及能够稳定地发挥其电化学性能。
在一些实施例中，在式I中，0.3≤a≤0.4，0.2≤b≤0.3，0.15≤c≤0.2，0.05≤d≤0.1，0.05≤e≤0.1，a+b+c+d+e＝1，0.4≤(b+c)/(a+d+e)≤1。
可选地，a为0.4，b为0.2，c为0.2，d为0.1，e为0.1。
在这些可选的实施例中，各元素的配比满足上述要求的含锑的钠复合氧化物中能够提高层状结构中阳离子的排列有序程度，保证了正极活性材料具有较高的结 构稳定性，从而使得正极活性材料对水稳定性更强。另一方面，根据这些可选的实施例，含锑的钠复合氧化物可以包含较高含量的Fe和Ni，以使得使用这样的正极活性材料的钠离子电池具有更高的首次充放电比容量。因此，根据本实施例的含锑的钠复合氧化物更好地兼顾了对水稳定性、电化学过程中的循环稳定性以及首次充放电比容量。
在一些实施例中，L选自Cu、Li、Ti、Zr、Mg、Ca、Zn、Bi、Sn、Al、Si、La、Ta、P和B中的一种或几种。
可选地，L选自Cu、Li、Mg、Zn、Al、Si和B中的一种或几种。
这些具体可选的附加掺杂元素能够增强层状的含锑的钠复合氧化物对水的稳定性，以及含锑的钠复合氧化物在电化学过程中的循环稳定性。而且，这些具体可选的L示例对电解液的稳定性好，而且还有利于电解液的浸润。
本申请的层状的含锑的钠复合氧化物作为正极活性材料，根据层状的含锑的钠复合氧化物的稳定相结构，可将其分类为P2相、O3相等层状金属氧化物。
在一些实施例中，含锑的钠复合氧化物包括O3相，O3相为具有空间群
Figure PCTCN2022105646-appb-000003
的层状晶体结构。
在这些可选的实施例中，O3相比于其他相在比容量和比能量两方面都具有较大的优势。本申请含锑的钠复合氧化物包括O3相，O3相为具有空间群
Figure PCTCN2022105646-appb-000004
的层状晶体结构，具有该种晶体结构的正极活性材料，其结构稳定性好，有利于提高正极活性材料的容量性能及循环性能。
在一些实施例中，含锑的钠复合氧化物的层间距为0.53nm～0.54nm。
可选地，含锑的钠复合氧化物的层间距为0.534nm～0.548nm。
在这些可选的实施例中，含锑的钠复合氧化物的层间距(d 003)控制在此范围内时，正极活性材料的结构更加稳定，表现为正极活性材料的循环性能更好。同时钠离子在层间更容易脱嵌，更好地提高正极活性材料的充放电比容量。此外，含锑的钠复合氧化物的层间距在0.53nm～0.54nm之间，有利于钠离子在层间的传导扩散，又能抑制层状含锑的钠复合氧化物遇水时氢离子与钠离子发生交换反应，从而使得含锑的钠复合氧化物对水具有更高的稳定性。
在一些实施例中，含锑的钠复合氧化物的X射线衍射谱满足I 1/I 0≥0.2，
其中，I 1为在去离子水浸泡24h后的含锑的钠复合氧化物的O3相003晶面 的X射线衍射峰的峰强度，I 0为未在去离子水内浸泡的含锑的钠复合氧化物的O3相003晶面的X射线衍射峰的峰强度。
在本申请一些实施例中，含锑的钠复合氧化物的X射线衍射谱满足0.2≤I 1/I 0＜1，I 1/I 0反映了O3相层含锑的钠复合氧化物对水的敏感程度。
可选地，含锑的钠复合氧化物的X射线衍射谱满足0.35≤I 1/I 0＜1。
更可选地，含锑的钠复合氧化物的X射线衍射谱满足0.6≤I 1/I 0≤0.9。
图1是本申请一实施方式的正极活性材料在去离子水浸泡24h前后的X射线衍射谱；图2是本申请另一实施方式的正极活性材料在去离子水浸泡24h前后的X射线衍射谱；图3是不含锑的正极活性材料在去离子水浸泡24h前后的X射线衍射谱。
作为示例，图1示出了含锑的钠复合氧化物NaNi 0.2Fe 0. 29Mn 0.4Cu 0.1Sb 0.01O 2在去离子水浸泡24h前后的X射线衍射谱。图1中实线部分为未在去离子水内浸泡(浸泡前)的含锑的钠复合氧化物的O3相的X射线衍射图线，虚线部分为该含锑的钠复合氧化物在去离子水内浸泡24h后(浸泡后)的X射线衍射图线。从图1可以看出，I 1/I 0为0.35，且两X射线衍射图中各特征峰的位置基本相同，说明含锑的钠复合氧化物NaNi 0.2Fe 0. 29Mn 0.4Cu 0.1Sb 0.01O 2在去离子水中浸泡24小时后其晶体结构没有发生实质变化，因此该含锑的钠复合氧化物对水不敏感，可以理解为其对水的稳定性强。
作为又一示例，图2示出了含锑的钠复合氧化物NaNi 0.2Fe 0.2Mn 0.4Cu 0.1Sb 0.1O 2在去离子水浸泡24h前后的X射线衍射谱。图2中实线部分为未在去离子水内浸泡(浸泡前)的含锑的钠复合氧化物的O3相的X射线衍射图线，虚线部分为该含锑的钠复合氧化物在去离子水内浸泡24h后(浸泡后)的X射线衍射图线。从图2中可以看出，I 1/I 0为0.86，且两X射线衍射图中各特征峰的位置基本相同，说明含锑的钠复合氧化物NaNi 0.2Fe 0.2Mn 0.4Cu 0.1Sb 0.1O 2在去离子水中浸泡24小时后其晶体结构没有发生实质变化，因此该含锑的钠复合氧化物对水不敏感，其对水稳定性更强。
作为对比，图3示出了不含锑的钠复合氧化物NaNi 0.2Fe 0.29Mn 0.4Cu 0.11O 2在去离子水浸泡24h前后的X射线衍射谱。图3中实线部分为未在去离子水内浸泡(浸泡前)的钠复合氧化物的O3相晶体的X射线衍射图线，虚线部分为该钠复合氧化物在去离子水内浸泡24h后(浸泡后)的X射线衍射图线。从图3中可以看出，I 1/I 0为 0.08，且两X射线衍射图中各特征峰的位置出现偏差，说明该不含有锑的钠复合氧化物在去离子水中浸泡24小时后其晶体结构发生显著变化，因此该不含锑的钠复合氧化物对水较为敏感，对水的稳定性差。
在这些可选的实施例中，采用锑进行掺杂增强了O3相层状含锑的钠复合氧化物中过渡金属和氧的相互作用力，从而增加了对水的稳定性，这体现在I 1/I 0参数上，I 1/I 0的比值越大，说明对水越不敏感，以表明含锑的钠复合氧化物对水的稳定性越强。
在一些实施例中，正极活性材料的体积平均粒径Dv50为3μm～30μm。
可选地，正极活性材料的体积平均粒径Dv50为5μm～15μm。
根据本申请，正极活性材料的体积平均粒径Dv50可以采用本领域的常规方式测量。例如可以参照GB/T 19077-2016粒度分布激光衍射法，采用激光粒度分析仪方便地测定，如英国马尔文仪器有限公司的Mastersizer 2000E型激光粒度分析仪。
在这些可选的实施例中，正极活性材料的体积平均粒径Dv50在适当范围内，有利于使正极活性材料层获得较高的压实密度，同时具有合适的孔隙率，来满足电化学反应所需的电解液浸润量，还具有较短的颗粒内活性离子和电子的迁移路径，由此能够提高正极活性材料层的能量密度和循环性能。
在一些实施例中，正极活性材料的比表面积为0.1m 2/g～5m 2/g。
可选地，正极活性材料的比表面积为0.3m 2/g～3m 2/g。
根据本申请，正极活性材料的比表面积为本领域公知的含义，可以用本领域公知的仪器及方法进行测定。例如可以参照GB/T 19587-2017气体吸附BET法测定固态物质比表面积标准，采用氮气吸附比表面积分析测试方法测试，并用BET(Brunauer Emmett Teller)法计算得出，其中氮气吸附比表面积分析测试可以通过美国Micromeritics公司的Tri Star Ⅱ 3020型比表面与孔隙分析仪进行。
在这些可选的实施例中，正极活性材料的具有适当的比表面积，能够减少正极浆料制备过程中的吸液现象，提高正极浆料中的固含量及颗粒分散均匀性，从而能够提高包含正极活性材料的膜层中颗粒分散均匀性和压实密度，进而提高钠离子电池的比容量和能量密度，并改善钠离子电池的循环性能。
在一些实施例中，正极活性材料的振实密度为1g/cm 3～3g/cm 3。
可选地，正极活性材料的振实密度为1.5g/cm 3～2.5g/cm 3。
根据本申请，正极活性材料的振实密度为本领域公知的含义，可以用本领域公知的仪器及方法进行测定，例如可以参照GB/T5162-2006粉末振实密度测定方法，通过振实密度测定仪进行，如FZS4-4B型振实密度测定仪。
在这些可选的实施例中，正极活性材料具有适当的振实密度，有利于使正极活性材料具有较高的压实密度，从而使钠离子电池具有较高的容量性能及能量密度。
在一些实施例中，正极活性材料在8吨压力下的粉体压实密度为3g/cm 3～5g/cm 3，可选地为3.5g/cm 3～4.5g/cm 3。
根据本申请，正极活性材料的压实密度为本领域公知的含义，可以用本领域公知的仪器及方法进行测定，例如可以参照GB/T24533-2009标准，通过电子压力试验机进行，如UTM7305型电子压力试验机。
在这些可选的实施例中，正极活性材料具有较高的压实密度，有利于使钠离子电池具有较高的容量性能及能量密度。在此范围内，正极活性材料的压实密度越高，钠离子电池的容量性能及能量密度相应地越高。
正极活性材料的制备方法
正极活性材料的制备方法，包括：
提供原料，使得原料中的元素配比满足本申请第一方面的式I所示的化学式；
将原料进行煅烧处理，得到正极活性材料，
其中，正极活性材料包括层状的含锑的钠复合氧化物，含锑的钠复合氧化物具有如式I所示的化学式，
Na xMn aFe bNi cSb dL eO 2   (I)
在式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d＜0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
在一些实施例中，正极活性材料的原料可以通过共沉淀法、凝胶法或固相法制备获得。
根据本申请的正极活性材料制备方法的实施例，先提供原料，再将原料煅烧，得到正极活性材料。上述正极活性材料的制备方法简单，且可制造性高。
在一些实施例中，步骤S1提供原料包括：将钠源、锰源、铁源、镍源、锑源和L源搅拌均匀，获得原料。S1中可以采用球磨混合机或高速混合机来进行混合。作为一个示例，按照化学计量比将钠源、锰源、铁源、镍源、锑源和L源加入高速混合机中进行混合，混料时间为0.5h～2h。通过固相混合方法，使钠源、锰源、铁源、镍源、锑源和L源进行混合，从而得到原料。
在本申请一些实施例中，L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种。
在本申请一些实施例中，钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种。
在本申请一些实施例中，铁源选自Fe 2O 3、Fe 3O 4和FeO中的一种或几种。
在本申请一些实施例中，锰源选自Mn 2O 3、Mn 3O 4、MnO和MnO 2中的一种或几种。
在本申请一些实施例中，镍源选自NiO或Ni(OH) 2。
在本申请一些实施例中，锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种。
在又一些实施例中，步骤S1提供原料包括：将铁源、锰源、镍源、L源与水混合，获得混合液；将混合液与沉淀剂混合，形成沉淀物；将沉淀物、钠源和锑源搅拌均匀，获得原料。通过共沉淀方法，使锰源、铁源、镍源和L源进行沉淀，再与钠源和锑源通过球磨混合机或高速混合机来进行混合，从而得到原料。
在本申请一些实施例中，L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种；
在本申请一些实施例中，钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种。
在本申请一些实施例中，铁源选自含铁的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请一些实施例中，锰源选自含锰的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请一些实施例中，镍源选自含镍的氯化物、硫酸盐和硝酸盐中的一种或几种。
在本申请一些实施例中，锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种。
在本申请一些实施例中，沉淀剂选自氢氧化物、碳酸盐和草酸盐中的一种或几种。
在一些实施例中，步骤S2中煅烧包括将原料在马弗炉中进行煅烧处理，煅烧温度为600℃～1200℃，气氛为空气或氧气气氛，保温时间为10h～20h。煅烧温度对正极活性材料的性能影响较大，当煅烧温度较低时，反应不完全，容易生成无定形材料，且含有杂相，对正极活性材料的电化学性能影响较大。随着煅烧温度较的升高，物料的扩散系数增大，促进了离子和空位的扩散、颗粒重排等物质传递过程，从而有利于得到结构稳定性高的产物。当煅烧温度较高时，容易生成缺氧型化合物，且不利于钠离子在正极活性材料中的脱出和嵌入。
可选地，煅烧温度为900℃～950℃，保温时间为15h～20h。
可选地，可根据需要在煅烧之前进行预煅烧，预煅烧的温度为600℃～900℃，气氛为空气或氧气气氛，保温时间为10h～20h。
在本申请一些实施例中，步骤S2中煅烧后还包括降温后进行机械粉碎处理，获得正极活性材料。如此，使得正极活性材料的体积平均粒径Dv50为3μm～30μm。有利于使最终得到的正极活性材料具有较优的粒度分布和比表面积。
另外，以下适当参照附图4至图9，对本申请的二次电池、电池模块、电池包和用电装置进行说明。图4是本申请一实施方式的二次电池的示意图。图5是图4所示的本申请一实施方式的二次电池的分解图。图6是本申请一实施方式的电池模块的示意图。图7是本申请一实施方式的电池包的示意图。图8是图7所示的本申请一实施方式的电池包的分解图。图9是本申请一实施方式的二次电池用作电源的用电装置的示意图。
本申请的第三方面提供一种二次电池，包括本申请第一方面的正极活性材料或通过本申请第二方面的制备方法制得的正极活性材料。
通常情况下，二次电池包括正极极片、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。
正极极片包括正极集流体及形成于所述正极集流体的至少部分表面上的正极膜层，所述正极膜层包括正极活性材料，所述正极活性材料为本申请第一方面的正极活性材料或通过本申请第二方面的制备方法制得的正极活性材料。因此，前面对于根据本申请的正极活性材料的实施例的描述同样适用于二次电池中的正极活性材料，相同的内容不再赘述。
在一些实施例中，正极膜层还可以包括导电剂，以改善正极的导电性能。本申请对导电剂的种类不做具体限制，可以根据实际需求进行选择。作为示例，导电剂可以为超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种。
在一些实施例中，正极膜层还可以包括粘结剂，以将正极活性材料和可选的导电剂牢固地粘结在正极集流体上。本申请对粘结剂的种类不做具体限制，可以根据实际需求进行选择。作为示例，粘结剂可以为聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚丙烯酸(PAA)、聚乙烯醇(PVA)、乙烯-醋酸乙烯酯共聚物(EVA)、丁苯橡胶(SBR)、羧甲基纤维素(CMC)、海藻酸钠(SA)、聚甲基丙烯酸(PMA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施例中，正极集流体可以采用导电碳片、金属箔材、涂炭金属箔材、多孔金属板或复合集流体，其中导电碳片的导电碳材质可以为超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种，金属箔材、涂炭金属箔材和多孔金属板的金属材质各自独立地可以选自铜、铝、镍及不锈钢中的至少一种。复合集流体可以为金属箔材与高分子基膜复合形成的复合集流体。正极集流体例如为铜箔、铝箔、镍箔、不锈钢箔、不锈钢网及涂炭铝箔中的一种或几种，优选采用铝箔。
以按照本领域常规方法制备上述正极极片。通常将正极活性材料及可选的导电剂和粘结剂分散于溶剂(例如N-甲基吡咯烷酮，简称为NMP)中，形成均匀的正极浆料，将正极浆料涂覆在正极集流体上，经烘干、冷压后，得到正极极片。
在本申请的一些实施例中，负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施例中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。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(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)等的基材)上而形成。
在一些实施例中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施例中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施例中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、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。
在一些实施例中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施例中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
在本申请的一些实施例中，电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施例中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施例中，电解质盐可选NaPF 6、NaClO 4、NaBF 4、KPF 6、KClO 4、KBF 4、LiPF 6、LiClO 4、LiBF 4、Zn(PF 6) 2、Zn(ClO 4) 2、Zn(BF 4) 2中的一种或几种。
在一些实施例中，电解质盐可选自NaPF 6、NaClO 4、NaBF 4中的一种或几种。
在一些实施例中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施例中，所述电解液还可选地包括添加剂。例如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、改善电池高温或低温性能的添加剂等。
在本申请的一些实施例中，对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施例中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施例中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施例中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施例中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次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。例如，图4示出了作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图5，外包装可包括壳体51和盖板53。其中，壳体51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51具有与容纳腔连通的开口，盖板53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52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池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。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次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6示出了作为一个示例的电池模块4。参照图6，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5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7和图8示出了作为一个示例的电池包1。参照图7和图8，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。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置 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。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图9示出了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二次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。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
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
将Na 2CO 3、NiO、Mn 2O 3、CuO、Sb 2O 3按照投料主元素摩尔比Na∶Mn∶Ni∶Cu∶Sb＝1∶0.2∶0.5∶0.2∶0.1，称量各样品总计30g。将各样品在玛瑙研钵中预先研磨后，再加入到行星球磨机中球磨1h，获得原料。将原料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℃恒温下保温15h，自然降温，获得正极活性材料，其中，正极活性材料为层状NaNi 0.2Mn 0.5Cu 0.2Sb 0.1O 2。
将实施例1～19和对比例1～6的正极活性材料按照下表1进行制备。
表1实施例1～19与对比例1～6的正极活性材料的参数结果
Figure PCTCN2022105646-appb-000005
Figure PCTCN2022105646-appb-000006
钠离子电池的制造
(1)正极极片的制备
将上述正极活性材料与导电炭黑(SP)、粘结剂聚偏二氟乙烯(PVDF)按80∶15∶5重量比在适量的N-甲基吡咯烷酮(NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料；将此浆料涂覆于正极集流体涂炭Al箔上，干燥、冷压后冲成直径为14mm的小圆片。
(2)电解液的制备
将等量体积的碳酸乙烯酯溶解在碳酸丙烯酯中，然后将适量的高氯酸钠均匀溶解在混合溶剂中形成1mol/L的电解液，备用。
(3)负极极片采用金属钠片。
(4)隔离膜选用多孔聚乙烯膜。
(5)将正极极片、隔离膜、负极极片按顺序堆叠并卷绕，得到电极组件。将电极组件放入外包装中，加入上述制备的电解液，经封装、静置、化成、老化等工序后，得到二次电池。
按照如下的测试方法测试各实施例和对比例的正极活性材料和二次电池的。
(1)正极活性材料的003晶面的层间距d 003及空间群测试
在干燥房或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
Figure PCTCN2022105646-appb-000007
扫描2θ角范围为10°～70°，扫描速率为4°/min进行测试，测试完成后通过003晶面对应的角度，根据布拉格方程2d·sinθ＝λ，以及003晶面每个晶胞包含三层过渡金属层，即可得到003晶面的层间距d 003，通过样品的XRD衍射峰与XRD分析软件的标准卡片对比，可确认样品的空间群。
(2)正极活性材料的浸泡测试
取5g正极活性材料置于烧杯中，加入15mL去离子水并剧烈搅拌1min，静置24h后抽滤，并在60℃下真空干燥6h，得到浸泡后的正极活性材料。
使用上述测试(1)中的X射线粉末衍射仪观察在水中浸泡24h前后正极活性材料的X射线衍射谱中(003)特征峰强度变化。I 1表示正极活性材料在水中浸泡24h后X射线衍射谱中(003)特征峰强度，I 0表示正极活性材料浸泡前X射线衍射谱中(003)特征峰强度。I 1/I 0可以表示正极活性材料的水稳定型，I 1/I 0越小，正极活性材料的水稳定性越差，对水越敏感。
(3)高湿存储的容量变化率测试
将上述实施例制备的正极活性材料在湿度70％、温度25℃空气的环境下放置一天，与上述正极活性材料在常规存储条件下放置一天(湿度<1％、温度25℃)，将两种存储条件的正极活性材料分别制成电池，并测试其容量，计算正极活性材料的高湿存储容量变化率。
具体为：25℃下，将正极活性材料制备成二次电池后，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1.5V，得到二次电池的放电比容量C 0。把相同的正极活性材料在湿度70％，温度25℃空气放置一天后，25℃下，将所得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1.5V，得到二次电池的放电比容量C 1，其中，变化率＝C 1/C 0。
表2实施例1～19与对比例1～6的测试结果
Figure PCTCN2022105646-appb-000008
根据上述结果可知，实施例1至19，均取得了良好的效果，层间距适中、I 1/I 0值大，且正极活性材料的比表面积为、振实密度和在8吨压力下的粉体压实密度均 较高，而且高湿存储的容量变化率高，变化率越高说明对水稳定性越好。本申请的通过掺杂有特定金属Sb能够使得层状含锑的钠复合氧化物对水具有较高稳定性，并且，在电化学反应过程中，能够有效地的抑制含锑的钠复合氧化物发生副反应，从而获得了较高的比表面积为、振实密度和在8吨压力下的粉体压实密度，进而使得包含本申请的正极活性材料的钠离子电池的首次充放电的比容量较高。
对比例1，不包含锑掺杂的正极活性材料，正极活性材料的I 1/I 0值小，说明正极活性材料对水稳定性较差。对比例2、3和4，掺杂Fe和Ni的含量过高，过多的Fe和Ni更容易与水发生反应，使得正极活性材料的I 1/I 0值小，说明正极活性材料对水稳定性较差。正极活性材料包含较低含量的Fe和Ni，以使得使用这样的正极活性材料的钠离子电池具有较低的首次充放电比容量，还会降低层状含锑的钠复合氧化物层间的结构稳定性。对比例5和对比例6表明，避免Sb掺杂过多，导致钠离子电池具有降低的首次充放电比容量，Sb掺杂过少，无法满足正极材料对水的稳定性。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。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 (16)

  1. 一种正极活性材料，包括层状的含锑的钠复合氧化物，所述含锑的钠复合氧化物具有如式I所示的化学式，
    Na xMn aFe bNi cSb dL eO 2  (I)
    在所述式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d≤0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
  2. 根据权利要求1所述的正极活性材料，其中，
    在所述式I中，0.3≤a≤0.4，0.2≤b≤0.3，0.15≤c≤0.2，0.05≤d≤0.1，0.05≤e≤0.1，a+b+c+d+e＝1，0.4≤(b+c)/(a+d+e)≤1。
  3. 根据权利要求1或2所述的正极活性材料，其中，
    所述L选自Cu、Li、Ti、Zr、Mg、Ca、Zn、Bi、Sn、Al、Si、La、Ta、P和B中的一种或几种，可选地，L选自Cu、Li、Mg、Zn、Al、Si和B中的一种或几种。
  4. 根据权利要求1至3中任一项所述的正极活性材料，其中，
    所述含锑的钠复合氧化物包括O3相，所述O3相为具有空间群
    Figure PCTCN2022105646-appb-100001
    的层状晶体结构。
  5. 根据权利要求1至4中任一项所述的正极活性材料，其中，
    所述含锑的钠复合氧化物的层间距为0.53nm～0.54nm。
  6. 根据权利要求1至5中任一项所述的正极活性材料，其中，
    所述含锑的钠复合氧化物的X射线衍射谱满足I 1/I 0≥0.2，
    其中，I 1为在去离子水浸泡24h后的所述含锑的钠复合氧化物的O3相003晶面的X射线衍射峰的峰强度，I 0为未在去离子水内浸泡的所述含锑的钠复合氧化物的O3相003晶面的X射线衍射峰的峰强度。
  7. 根据权利要求1至6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下述(1)～(4)中的一个或几个：
    (1)所述正极活性材料的体积平均粒径Dv50为3μm～30μm，可选为5μm～15μm；
    (2)所述正极活性材料的比表面积为0.1m 2/g～5m 2/g，可选为0.3m 2/g～3m 2/g；
    (3)所述正极活性材料的振实密度为1g/cm 3～3g/cm 3，可选为1.5g/cm 3～2.5g/cm 3；
    (4)所述正极活性材料在8吨压力下的粉体压实密度为3g/cm 3～5g/cm 3，可选地为3.5g/cm 3～4.5g/cm 3。
  8. 一种正极活性材料的制备方法，包括：
    提供原料，使得所述原料中的元素配比满足权利要求1至7任一项所述的式I所示的化学式；
    将所述原料进行煅烧处理，得到正极活性材料，
    其中，所述正极活性材料包括层状的含锑的钠复合氧化物，所述含锑的钠复合氧化物具有如式I所示的化学式，
    Na xMn aFe bNi cSb dL eO 2  (I)
    在所述式I中，0.7＜x≤1，0＜a，0≤b，0.1＜c≤0.3，0＜d＜0.1，0≤e，a+b+c+d+e＝1，(b+c)/(a+d+e)≤1，L选自Cu、Li、Ti、Zr、K、Nb、Mg、Ca、Mo、Zn、Cr、W、Bi、Sn、Ge、Al、Si、La、Ta、P和B中的一种或几种。
  9. 根据权利要求8所述的正极活性材料的制备方法，其中，
    所述提供原料包括：
    将钠源、锰源、铁源、镍源、锑源和L源搅拌均匀，获得原料，
    其中，所述L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种。
  10. 根据权利要求8或9所述的正极活性材料的制备方法，其中，
    所述原料满足下述(5)～(9)中的一个或几个：
    (5)所述钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种；
    (6)所述铁源选自Fe 2O 3、Fe 3O 4和FeO中的一种或几种；
    (7)所述锰源选自Mn 2O 3、Mn 3O 4、MnO和MnO 2中的一种或几种；
    (8)所述镍源选自NiO或Ni(OH) 2；
    (9)所述锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种。
  11. 根据权利要求8至10中任一项所述的正极活性材料的制备方法，其中，
    所述提供原料包括：
    将铁源、锰源、镍源、L源与水混合，获得混合液，其中，所述L源选自Cu源、Li源、Ti源、Zr源、K源、Nb源、Mg源、Ca源、Mo源、Zn源、Cr源、W源、Bi源、Sn源、Ge源、Al源、Si源、La源、Ta源、P源和B源中的一种或几种；
    将所述混合液与沉淀剂混合，形成沉淀物；
    将所述沉淀物、钠源和锑源搅拌均匀，获得原料。
  12. 根据权利要求11所述的正极活性材料的制备方法，其中，
    所述原料满足下述(10)～(15)中的一个或几个：
    (10)所述钠源选自Na 2CO 3、NaHCO 3、NaOH和Na 2O 2中的一种或几种；
    (11)所述铁源选自含铁的氯化物、硫酸盐和硝酸盐中的一种或几种；
    (12)所述锰源选自含锰的氯化物、硫酸盐和硝酸盐中的一种或几种；
    (13)所述镍源选自含镍的氯化物、硫酸盐和硝酸盐中的一种或几种；
    (14)所述锑源选自单质锑、含锑的氧化物或锑盐中的一种或几种；
    (15)所述沉淀剂选自氢氧化物、碳酸盐和草酸盐中的一种或几种。
  13. 一种二次电池，其特征在于，包括权利要求1～7中任一项所述的正极活性材料或通过权利要求8～12中任一项所述的正极活性材料的制备方法制得的正极活性材料。
  14. 一种电池模块，包括权利要求13所述的二次电池。
  15. 一种电池包，包括权利要求14所述的电池模块。
  16. 一种用电装置，包括选自权利要求13所述的二次电池、权利要求14所述的电池模块或权利要求15所述的电池包中的至少一种。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119118207A (zh) * 2024-11-15 2024-12-13 天津理工大学 高循环稳定性钠离子电池正极材料及其制备方法和应用

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118645618B (zh) * 2024-06-28 2025-04-18 北京当升材料科技股份有限公司 正极活性材料及其制备方法、正极极片、电池及用电设备
WO2026007032A1 (zh) * 2024-07-03 2026-01-08 万华化学(烟台)电池材料科技有限公司 一种正极活性材料及其制备方法与应用
CN120767376A (zh) * 2024-09-03 2025-10-10 宁德时代新能源科技股份有限公司 正极活性材料、钠二次电池及用电装置
CN121790378A (zh) * 2024-09-30 2026-04-03 宁德时代新能源科技股份有限公司 电池单体及其制备方法、正极活性材料及其制备方法、正极极片、电池装置和用电装置
CN119340372A (zh) * 2024-11-11 2025-01-21 华南理工大学 一种双金属Sb和Al共掺杂协同改性O3型镍锰基钠离子电池正极材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328928A (zh) * 2016-11-07 2017-01-11 中国科学院化学研究所 一类钠离子电池正极材料、其制备方法及提高空气稳定性的方法
CN111268746A (zh) * 2020-02-05 2020-06-12 中国科学院化学研究所 一种钠离子电池层状正极材料、制备方法及其应用
CN111564615A (zh) * 2020-05-11 2020-08-21 中国科学院化学研究所 非金属掺杂正极、二次掺杂正极及制备方法
CN113258060A (zh) * 2020-02-11 2021-08-13 中国科学院物理研究所 一种钠离子电池高镍层状氧化物材料及其制备方法和应用
CN114207878A (zh) * 2019-06-24 2022-03-18 法国国家科研中心 用于钠离子电池组的层状活性材料

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934597A (zh) * 2015-06-25 2015-09-23 中国科学院化学研究所 一类钠离子电池正极材料的制备及应用
CN111435742A (zh) * 2019-01-11 2020-07-21 宁德时代新能源科技股份有限公司 正极活性材料、正极极片及钠离子电池
CN119905574A (zh) * 2019-09-27 2025-04-29 宁德时代新能源科技股份有限公司 钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置
PL3951943T3 (pl) * 2020-03-27 2024-04-02 Contemporary Amperex Technology Co., Limited Bateria wtórna i aparat zawierający baterię wtórną
CN116802872A (zh) * 2021-12-29 2023-09-22 宁德时代新能源科技股份有限公司 层状氧化物正极活性材料、以及包含其的正极极片、钠离子电池及用电装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328928A (zh) * 2016-11-07 2017-01-11 中国科学院化学研究所 一类钠离子电池正极材料、其制备方法及提高空气稳定性的方法
CN114207878A (zh) * 2019-06-24 2022-03-18 法国国家科研中心 用于钠离子电池组的层状活性材料
CN111268746A (zh) * 2020-02-05 2020-06-12 中国科学院化学研究所 一种钠离子电池层状正极材料、制备方法及其应用
CN113258060A (zh) * 2020-02-11 2021-08-13 中国科学院物理研究所 一种钠离子电池高镍层状氧化物材料及其制备方法和应用
CN111564615A (zh) * 2020-05-11 2020-08-21 中国科学院化学研究所 非金属掺杂正极、二次掺杂正极及制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENGLONG ZHAO; FEIXIANG DING; YAXIANG LU; LIQUAN CHEN; YONG‐SHENG HU: "High‐Entropy Layered Oxide Cathodes for Sodium‐Ion Batteries", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 59, no. 1, 19 November 2019 (2019-11-19), Hoboken, USA, pages 264 - 269, XP072087723, ISSN: 1433-7851, DOI: 10.1002/anie.201912171 *
See also references of EP4336592A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119118207A (zh) * 2024-11-15 2024-12-13 天津理工大学 高循环稳定性钠离子电池正极材料及其制备方法和应用

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