WO2024217014A1 - 钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置 - Google Patents

钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置 Download PDF

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WO2024217014A1
WO2024217014A1 PCT/CN2023/138238 CN2023138238W WO2024217014A1 WO 2024217014 A1 WO2024217014 A1 WO 2024217014A1 CN 2023138238 W CN2023138238 W CN 2023138238W WO 2024217014 A1 WO2024217014 A1 WO 2024217014A1
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positive electrode
active material
electrode active
sodium
battery
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French (fr)
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唐正
叶永煌
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/485—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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 present application relates to the field of batteries, and more specifically, to a positive electrode active material, a positive electrode sheet, a battery cell, a sodium metal battery and an electrical device of a sodium metal battery.
  • Sodium metal batteries are secondary batteries that use metallic sodium directly as the negative electrode active material. Due to the abundant reserves of sodium on the earth, sodium metal batteries have become energy storage devices with great development potential. Therefore, how to improve the energy density of sodium metal batteries has become a technical problem that needs to be solved urgently.
  • the present application is made in view of the above-mentioned technical problems, and its purpose is to provide a positive electrode active material, a positive electrode plate, a battery cell, a sodium metal battery and an electrical device for a sodium metal battery.
  • the positive electrode active material is used in a sodium metal battery, the energy density of the sodium metal battery can be improved.
  • a positive electrode active material for a sodium metal battery comprising: a sodium transition metal oxide and a polyanionic compound; wherein the specific surface area of the sodium transition metal oxide satisfies: 0.4m 2 /g ⁇ BET 1 ⁇ 4.0m 2 /g, and the specific surface area of the polyanionic compound satisfies: 10m 2 /g ⁇ BET 2 ⁇ 20m 2 /g.
  • the positive electrode active material includes a sodium transition metal oxide and a polyanionic compound, wherein the sodium transition metal oxide has a higher capacity and the polyanionic compound has a better power performance.
  • the sodium transition metal oxide has a higher capacity and a higher power.
  • the powder compaction density of the compounded positive electrode active material can be improved, thereby improving the energy density of the sodium metal battery while also helping to improve the capacity and power performance of the sodium metal battery.
  • the powder compaction density of the positive electrode active material under a pressure of 29400N satisfies: 1.8 g/cm 3 ⁇ 2.8 g/cm 3 .
  • the ratio of the mass m 1 of the sodium transition metal oxide to the mass m 2 of the polyanionic compound satisfies: 1/9 ⁇ m 1 /m 2 ⁇ 1.
  • the ratio of the mass m 1 of the sodium transition metal oxide to the mass m of the positive electrode active material satisfies: 0.1 ⁇ m 1 /m ⁇ 0.5.
  • the ratio of the mass m 2 of the polyanionic compound to the mass m of the positive electrode active material satisfies: 0.5 ⁇ m 2 /m ⁇ 0.9, and 0 ⁇ (m 1 +m 2 )/m ⁇ 1.
  • the anion in the polyanionic compound includes at least one of phosphate, pyrophosphate, fluoropyrophosphate, and sulfate.
  • the polyanionic compound includes NaxM1yPmOn ; wherein M1 represents a metal element, the metal element includes at least one of Mn, Fe, Co, Cu, Al, Ti, and V, 1 ⁇ x ⁇ 2 , 0 ⁇ y ⁇ 1, 0 ⁇ m ⁇ 2, 4 ⁇ n ⁇ 8, and 0 ⁇ x/m ⁇ 1.
  • the sodium transition metal oxide comprises Na a M2 b O c ; wherein M2 represents a transition metal element, 0.3 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 1, 2 ⁇ c ⁇ 2.1.
  • the transition metal element includes at least one of Ni, Mn, Fe, Co, Cu, Ti, Cr, V, and Zn.
  • a positive electrode plate of a sodium metal battery wherein the positive electrode plate comprises a positive electrode active material as in any embodiment of the first aspect.
  • a battery cell of a sodium metal battery wherein the battery cell comprises a positive electrode plate as in any embodiment of the second aspect.
  • a sodium metal battery comprising the battery cell in any one of the embodiments of the third aspect.
  • an electric device comprising any one of the embodiments of the third aspect.
  • FIG. 1 is a schematic diagram of a battery cell of a sodium metal battery according to an embodiment of the present application.
  • FIG. 2 is a schematic diagram of a battery module of a sodium metal battery according to an embodiment of the present application.
  • FIG. 3 is a schematic diagram of a sodium metal battery according to an embodiment of the present application.
  • FIG. 4 is another schematic diagram of a sodium metal battery according to an embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "ab” represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the “include” and “comprising” mentioned in this application are open-ended or closed-ended.
  • the “include” and “comprising” may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: 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).
  • 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.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • Sodium metal battery refers to a sodium ion battery whose negative electrode active material is metallic sodium.
  • Sodium transition metal oxide refers to a compound composed of sodium and an oxide containing a transition metal element, such as Fe, Co, Ni, Cu, Zn, V, Cr, Mn. Structurally, sodium transition metal oxides can have a layered structure, a tunnel structure, and the like.
  • Polyanionic compounds refer to a class of compounds containing tetrahedral or octahedral anionic units. According to the type of anion, it can be divided into a variety of different systems. For example, phosphate system, pyrophosphate system, fluoropyrophosphate system, sulfate system, mixed anion system, etc.
  • the polyanionic compound may be a compound having sodium ions, transition metal ions, and tetrahedral anion units (YO 4 ) d- .
  • the transition metal may be one or more of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce
  • Y may be one or more of P, S, and Si
  • d represents the valence state of (YO 4 ) d- .
  • the polyanionic compound may be a compound having sodium ions, transition metal ions, tetrahedral anion units (YO 4 ) d- and halogen anions.
  • the transition metal may be one or more of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce
  • Y may be one or more of P, S and Si
  • d represents the valence state of (YO 4 ) d-
  • the halogen may be one or more of F, Cl and Br.
  • the polyanionic compound may also be a compound having sodium ions, tetrahedral anion units (YO 4 ) d- , polyhedral units (ZO f ) g+ and optional halogen anions.
  • Y may be one or more of P, S and Si
  • d represents the valence state of (YO 4 ) d-
  • Z represents a transition metal, which may be one or more of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce
  • g represents the valence state of (ZO f ) g+
  • the halogen may be one or more of F, Cl and Br.
  • a battery cell typically includes a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator.
  • active ions are embedded and removed back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays the role of 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, mainly to prevent the positive and negative electrodes from short-circuiting, and at the same time to allow active ions to pass through.
  • the above-mentioned battery cell is also called a secondary battery.
  • sodium-ion batteries rely on the electrochemical reaction of sodium ions constantly being extracted and embedded between the positive and negative electrodes to achieve charging and discharging.
  • sodium ions are extracted from the positive electrode active material, moved and embedded into the negative electrode active material, and electrons flow from the positive electrode to the negative electrode through an external circuit; and during the discharge process, sodium ions are extracted from the negative electrode active material, moved and embedded into the positive electrode active material, and electrons flow from the negative electrode to the positive electrode through an external circuit.
  • Sodium metal battery is a special type of sodium ion battery, in which metallic sodium is directly used as the negative electrode active material.
  • hard carbon is usually used as the negative electrode active material, and the theoretical capacity of this material is relatively low.
  • Sodium metal has a theoretical capacity of 1166mAh/g, which enables the battery system with sodium metal as the negative electrode to have a higher energy density.
  • sodium metal batteries compared with ordinary sodium ion batteries, sodium metal batteries have higher voltage, longer cycle life and higher charge and discharge rate. Therefore, sodium metal batteries have become a new generation of secondary batteries with great development potential.
  • the research on sodium metal batteries focuses on negative electrode materials and electrolytes, and the positive electrode active materials are usually directly used from the positive electrode active materials of sodium ion batteries.
  • the positive electrode active materials in sodium ion batteries usually cannot provide the corresponding energy density, which limits the capacity of sodium metal batteries and affects the development of sodium metal batteries.
  • the present application provides a positive electrode active material for a sodium metal battery, which can contribute higher energy density to the sodium metal battery and help improve the capacity and power performance of the sodium metal battery.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces opposite to each other in its thickness direction, and the positive electrode film layer can be disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of 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 embodiment of the present application first provides a positive electrode active material for a sodium metal battery, comprising a sodium transition metal oxide and a polyanionic compound, wherein the specific surface area of the sodium transition metal oxide satisfies: 0.4m 2 /g ⁇ BET 1 ⁇ 4.0m 2 /g, and the specific surface area of the polyanionic compound satisfies: 10m 2 /g ⁇ BET 2 ⁇ 20m 2 /g.
  • BET 1 can be 0.4 m 2 /g, 0.5 m 2 /g , 0.6 m 2 /g , 0.7 m 2 /g, 0.8 m 2 /g, 0.9 m 2 /g, 1.0 m 2 /g, 1.2 m 2 /g, 1.4 m 2 /g, 1.6 m 2 /g, 1.8 m 2 / g, 2.0 m 2 /g, 2.2 m 2 /g, 2.4 m 2 /g, 2.6 m 2 / g, 2.8 m 2 /g, 3.0 m 2 /g, 3.2 m 2 /g, 3.4 m 2 /g, 3.6 m 2 /g, 3.8 m 2 /g, 4.0 m 2 /g or a numerical range within the range obtained by combining any two of the above numerical values.
  • BET 2 may be 10m2 /g, 11m2 /g, 12m2 /g, 13m2 /g, 14m2 /g, 15m2 /g, 16m2 /g, 17m2/g , 18m2 /g, 19m2 /g, 20m2 /g, or a numerical range within the range obtained by combining any two of the above numerical values.
  • sodium transition metal oxide has a high capacity, but when used alone as a positive electrode active material, its structural stability is poor, which is not conducive to the long cycle of the battery.
  • Polyanionic compounds have a stable structure and a high operating voltage, which can provide a higher power for the battery, but when used alone as a positive electrode active material, the capacity is very limited and the energy density requirement of the sodium metal battery cannot be met.
  • the sodium metal battery can have both high capacity and power.
  • the powder compaction density of the positive electrode active material under a pressure of 29400N satisfies: 1.8 g/cm 3 ⁇ 2.8 g/cm 3 .
  • the powder compaction density ⁇ of the positive electrode active material under a pressure of 29400N can be 1.8g/ cm3 , 1.9g/ cm3 , 2.0g/ cm3 , 2.1g/ cm3 , 2.2g/ cm3 , 2.3g/ cm3 , 2.4g/ cm3 , 2.5g/ cm3 , 2.6g/ cm3 , 2.7g/ cm3 , 2.8g/ cm3 , or a numerical range within the range obtained by combining any two of the above numerical values.
  • the ratio of the mass m 1 of the sodium transition metal oxide to the mass m 2 of the polyanionic compound satisfies: 1/9 ⁇ m 1 /m 2 ⁇ 1.
  • m 1 /m 2 may be 1/9, 1/8, 1/7, 1/6, 1/5, 1/4, 1/3, 1/2, 1, or a numerical range thereof within a range obtained by combining any two of the above numerical values.
  • the ratio of the mass m 1 of the sodium transition metal oxide to the mass m of the positive electrode active material satisfies: 0.1 ⁇ m 1 /m ⁇ 0.5.
  • m 1 /m can be 0.1, 0.2, 0.3, 0.4, 0.5, or a value within the above range. Any combination of two values is within the range obtained.
  • the ratio of the mass m 2 of the polyanionic compound to the mass m of the positive electrode active material satisfies: 0.5 ⁇ m 2 /m ⁇ 0.9, and 0 ⁇ (m 1 +m 2 )/m ⁇ 1.
  • m 2 /m may be 0.5, 0.6, 0.7, 0.8, 0.9, or a numerical range thereof within the range obtained by combining any two of the above numerical values.
  • the anions in the polyanionic compound include at least one of phosphate, pyrophosphate, fluoropyrophosphate and sulfate.
  • the polyanionic compound includes NaxM1yPmOn ; wherein M1 represents a metal element, the metal element includes at least one of Mn, Fe, Co, Cu, Al, Ti, and V, 1 ⁇ x ⁇ 2 , 0 ⁇ y ⁇ 1, 0 ⁇ m ⁇ 2, 4 ⁇ n ⁇ 8, and 0 ⁇ x/m ⁇ 1.
  • the sodium transition metal oxide includes Na a M2 b O c ; wherein M2 represents a transition metal element, 0.3 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 1, 2 ⁇ c ⁇ 2.1.
  • the transition metal element includes at least one of Ni, Mn, Fe, Co, Cu, Ti, Cr, V, and Zn.
  • the positive electrode film layer may further include a binder.
  • 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 polytetrafluoroethylene
  • vinylidene fluoride-tetrafluoroethylene-propylene terpolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer
  • the positive electrode film layer includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as NMP) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as NMP
  • the negative electrode sheet generally includes a negative electrode current collector, or includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
  • the negative electrode plate of the sodium metal battery is the negative electrode current collector, that is, the negative electrode current collector directly serves as the negative electrode plate.
  • This type of sodium metal battery can also be called a "negative electrode-free battery”.
  • sodium ions released from the positive electrode sheet are deposited on the negative electrode current collector to form a sodium metal negative electrode, in which sodium metal is the negative electrode active material.
  • a conductive film layer can be provided on the negative electrode current collector.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer may be 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.
  • a metal foil a copper foil may be used.
  • 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 substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of 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 negative electrode active material may be a negative electrode active material for a sodium metal battery known in the art.
  • the negative electrode active material may include at least one of the following materials: sodium metal, a carbon-based material or metal deposited with sodium metal, an alloy material, a composite material containing sodium metal, an alloy material containing sodium metal, etc.
  • the present application is not limited to these materials, and other materials that can be used as negative electrode active materials for sodium metal batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more materials.
  • the negative electrode sheet can be prepared according to conventional methods in the art.
  • a copper foil or a copper foil with a conductive film layer disposed on at least one surface of the copper foil can be used as the negative electrode sheet.
  • the conductive film layer can be disposed on at least one surface of the negative electrode current collector by methods such as physical vapor deposition (PVD), spin coating, electroplating, and chemical vapor deposition (CVD).
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
  • the electrolyte salt includes NaPF 6 , NaBCl 4 , NaSO 3 CF 3 , and Na(CH 3 )C 6 H 4 SO 3 , and the like.
  • the solvent includes carbonate or ether solvents.
  • Carbonate solvents include cyclic ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC) and chain dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), etc.
  • ether solvents include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,3-dioxolane, etc.
  • the electrolyte may further include additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the sodium metal battery further includes a separator.
  • the separator may be a separator membrane.
  • the separator membrane may be any known porous structure separator membrane with good chemical stability and mechanical stability.
  • 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 membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the embodiments of the present application also provide a sodium metal battery cell, which includes the positive electrode plate in any embodiment of the present application.
  • the positive electrode sheet, the negative electrode sheet and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the battery cell may include an outer packaging, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the battery cell may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the battery cell may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG1 is a battery cell 100 of a sodium metal battery with a square structure as an example.
  • FIG2 is a battery module 200 of a sodium metal battery as an example.
  • the plurality of battery cells 100 may be arranged in sequence along the length direction of the battery module 200. Of course, they may also be arranged in any other manner. Further, the plurality of battery cells 100 may be fixed by fasteners.
  • the battery module 200 may further include a housing having an accommodation space, and the plurality of battery cells 100 are accommodated in the accommodation space.
  • the battery modules 200 may also be assembled into a sodium metal battery.
  • the number of battery modules 200 contained in the sodium metal battery may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery.
  • the sodium metal battery 300 may include a battery box and a plurality of battery modules 200 disposed in the battery box.
  • the battery box includes an upper box body 301 and a lower box body 302, and the upper box body 301 can be covered on the lower box body 302 to form a closed space for accommodating the battery modules 200.
  • the plurality of battery modules 200 can be arranged in the battery box in any manner.
  • the sodium metal battery 300 is also referred to as a sodium metal battery pack.
  • the battery cells 100 may first form a battery module 200, and the sodium metal battery 300 is composed of the battery module 200.
  • the sodium metal battery 300 may also be directly formed of the battery cells 100, omitting the intermediate form of the battery module 200.
  • the present application also provides an electrical device, which includes at least one of the battery cell 100 of the sodium metal battery, the battery module 200 of the sodium metal battery, or the sodium metal battery 300 provided in the present application.
  • the battery cell 100, the battery module 200, or the sodium metal battery 300 can be used as a power source for the electrical device, or as an energy storage unit for the electrical device.
  • the electrical 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, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • the number of battery cells 100, battery modules 200, or sodium metal batteries 300 can be selected according to the usage requirements.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a sodium metal battery 300 or a battery module 200 may be used.
  • the device may be a mobile phone, a tablet computer, a laptop computer, etc.
  • the device is usually required to be thin and light, and the battery cell 100 can be used as a power source.
  • the polyanionic compound NaFePO 4 , sodium transition metal oxide Na 0.95 Mn 0.33 Ni 0.33 Fe 0.33 O 2 , conductive carbon black (Super P) and binder PVDF were fully and uniformly mixed in a proper amount of NMP at a mass ratio of 45:45:5:5 to form a positive electrode slurry, which was then coated on a positive electrode current collector aluminum foil, and then dried and cold pressed to obtain a positive electrode sheet.
  • Carbon nanotubes and sodium alginate are added to deionized water and stirred to form a uniform slurry, which is then coated on copper foil, dried, and cold pressed to obtain a "negative electrode-free" negative electrode sheet, wherein the surface density of the coating is 20 g/m 2 .
  • the above-mentioned "negative electrode-free" electrode sheet after drying and cold pressing is cut, and the electrode sheet is assembled into a battery cell with the positive electrode sheet and the isolation membrane, and the assembled battery cell is charged to 3.8V at a constant current of 0.5C, so as to pre-deposit sodium metal on the electrode sheet; after the battery cell is fully charged, the fully charged electrode sheet is removed in the glove box and used as the negative electrode sheet.
  • the positive electrode sheet, glass fiber film and negative electrode sheet are stacked in order, and then wound to form an electrode assembly, which is then placed in a packaging shell, and 1M NaPF6 electrolyte is added. After packaging, formation, and standing, a sodium metal battery is obtained.
  • the solvent of the electrolyte is dimethyl ether (DME).
  • the positive electrode active material includes NaFePO 4 and Na 0.95 Mn 0.33 Ni 0.33 Fe 0.33 O 2 .
  • the positive electrode active material includes sodium Transition metal oxide NaMn 0.4 Fe 0.2 Ni 0.4 O 2 and polyanionic compound Na 2 FeP 2 O 7 .
  • BET 1 represents the specific surface area of the sodium transition metal oxide in the positive electrode active material
  • BET 2 represents the specific surface area of the polyanionic compound in the positive electrode active material
  • m 1 /m 2 represents the ratio of the mass m 1 of the sodium transition metal oxide in the positive electrode material to the mass m 2 of the polyanionic compound
  • m 1 /m represents the ratio of the mass m 1 of the sodium transition metal oxide in the positive electrode active material to the mass m of the positive electrode active material
  • m 2 /m represents the ratio of the mass m 2 of the polyanionic compound in the positive electrode material to the mass m of the positive electrode active material
  • ⁇ represents the powder compaction density of the positive electrode active material under a pressure of 29400N.
  • Example 1 Compared with using a polyanionic compound alone as a positive electrode active material, when a composite sodium transition metal oxide and a polyanionic compound are used as a positive electrode active material, under the same pressure, the powder compaction density of the positive electrode active material in Example 1 is significantly increased compared with the powder compaction density of the positive electrode active material in Comparative Example 1, and the energy density of the sodium metal battery in Example 1 is also significantly higher than that in Comparative Example 1. Therefore, it is explained that compounding the two materials of sodium transition metal oxide and polyanionic compound helps to increase the amount of active material that can be loaded on the pole piece per unit area, thereby improving the energy density of the sodium metal battery.
  • Example 1 compared with Example 1, the specific surface area of the sodium transition metal oxide in Comparative Example 2 is 10m 2 /g, which exceeds the range of 0.4m 2 /g-4m 2 /g; the specific surface area of the polyanionic compound is 30m 2 /g, which also exceeds the range of 10m 2 /g-20m 2 /g. It can be seen that the powder compaction density of the positive electrode active material in Example 1 is significantly higher than that of the powder compaction density of Comparative Examples 2-3, and the energy density of the sodium metal battery in Example 1 is also significantly higher than that of Comparative Examples 2-3.
  • the powder compaction density of the compounded positive electrode active material can be improved by controlling the specific surface areas of the two materials in a suitable range, thereby improving the energy density of the sodium metal battery. It is impossible to achieve the effect of improving the powder compaction density and energy density by simply compounding the two materials without controlling the powder compaction density within the above range.
  • test method refers to the standard GB/T19587-2004 "Determination of specific surface area of solid substances by gas adsorption BET method".
  • the powder compaction density of the material can be tested by methods known in the art.
  • GB/T 24533-2009 can be referred to and an electronic pressure testing machine (such as UTM7305) can be used for testing: a certain amount of powder is placed on a special compaction mold, different pressures are set, and the thickness of the powder under different pressures can be read on the equipment, and the compaction density under different pressures can be calculated.
  • UTM7305 electronic pressure testing machine

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Abstract

一种钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置，该正极活性材料包括钠过渡金属氧化物和聚阴离子型化合物；其中，钠过渡金属氧化物的比表面积满足：0.4m 2/g≤BET1≤4m 2/g，聚阴离子型化合物的比表面积满足：10m 2/g≤BET2≤20m 2/g。该正极活性材料有助于在实现高功率钠金属电池的同时，提高钠金属电池的能量密度。

Description

钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置
相关申请的交叉引用
本专利文件要求于2023年4月21日提交的发明名称为“钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置”的申请号为202310433077.7的中国专利申请的优先权和权益。上述专利申请的全部内容通过引用并入本专利文件公开内容的一部分。
技术领域
本申请涉及电池领域，更为具体地，涉及一种钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置。
背景技术
近年来，二次电池被广泛应用于水力、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，从而得到了极大的发展。
钠金属电池是将金属钠直接作为负极活性材料的二次电池，由于钠元素在地球上丰富的储量，使得钠金属电池成为了极具发展潜力的储能装置。因此，如何提高钠金属电池的能量密度成为一项亟待解决的技术问题。
发明内容
本申请是鉴于上述技术问题而进行的，其目的在于，提供一种钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池及用电装置，该正极活性材料应用于钠金属电池中时，能够提高钠金属电池的能量密度。
第一方面，提供一种钠金属电池的正极活性材料，包括：钠过渡金属氧化物和聚阴离子型化合物；其中，所述钠过渡金属氧化物的比表面积满足：0.4m2/g≤BET1≤4.0m2/g，所述聚阴离子型化合物的比表面积满足：10m2/g≤BET2≤20m2/g。
本申请的实施例中，正极活性材料包括钠过渡金属氧化物和聚阴离子型化合物，其中，钠过渡金属氧化物的容量较高而聚阴离子型化合物的功率性能较好。通过在聚阴离子型化合物中复配钠过渡金属氧化物，使得钠金属电池具有较高的容量以及较高的功率。通过控制两种材料的比表面积在合适的范围内，能够提升复配的正极活性材料的粉末压实密度，由此，在提高钠金属电池的能量密度的同时，还有助于提高钠金属电池的容量和功率性能。
在一些实施例中，所述正极活性材料在29400N压力下的粉末压实密度满足：1.8g/cm3≤ρ≤2.8g/cm3。
在一些实施例中，所述正极活性材料中，所述钠过渡金属氧化物的质量m1与所述聚阴离子型化合物的质量m2的比值满足：1/9≤m1/m2≤1。
在一些实施例中，所述钠过渡金属氧化物的质量m1与所述正极活性材料的质量m的比值满足：0.1≤m1/m≤0.5。
在一些实施例中，所述聚阴离子型化合物的质量m2与所述正极活性材料的质量m的比值满足：0.5≤m2/m≤0.9，且0＜(m1+m2)/m≤1。
在一些实施例中，所述聚阴离子型化合物中的阴离子包括磷酸根、焦磷酸根、氟代焦磷酸根、硫酸根中的至少一种。
在一些实施例中，所述聚阴离子型化合物包括NaxM1yPmOn；其中，M1表示金属元素，所述金属元素包括Mn、Fe、Co、Cu、Al、Ti、V中的至少一种，1≤x≤2，0＜y≤1，0＜m≤2，4≤n≤8，且0＜x/m≤1。
在一些实施例中，所述钠过渡金属氧化物包括NaaM2bOc；其中，M2表示过渡金属元素，0.3≤a≤1.2，0＜b≤1，2≤c≤2.1。
在一些实施例中，所述过渡金属元素包括Ni、Mn、Fe、Co、Cu、Ti、Cr、V、Zn中的至少一种。
第二方面，提供一种钠金属电池的正极极片，所述正极极片包括如第一方面任一实施例中的正极活性材料。
第三方面，提供一种钠金属电池的电池单体，所述电池单体包括如第二方面任一实施例中的正极极片。
第四方面，提供一种钠金属电池，所述钠金属电池包括第三方面任一实施例中的电池单体。
第五方面，提供一种用电装置，所述用电装置包括第三方面任一实施 例中的电池单体，和/或第四方面任一实施例中的钠金属电池。
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为本申请实施例一种钠金属电池的电池单体的示意图。
图2为本申请实施例一种钠金属电池的电池模块的示意图。
图3为本申请实施例一种钠金属电池的示意图。
图4为本申请实施例一种钠金属电池的另一示意图。
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钠金属电池的正极活性材料、正极极片、电池单体、钠金属电池以及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。
在本申请的描述中，需要说明的是，除非另有说明，“多个”的含义是两个以上；术语“上”、“下”、“左”、“右”、“内”、“外”等指示的方位或位置关系仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。此外，术语“第一”、“第二”、“第三”等仅用于描述目的，而不能理解为指示或暗示相对重要性。
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)。
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，以下术语具有以下含义。任何未定义的术语具有它们在技术上公认的含义。
“钠金属电池”指的是负极活性材料为金属钠的钠离子电池。
“钠过渡金属氧化物”指的是钠和含有过渡金属元素的氧化物组成的化合物，过渡金属元素例如可以是Fe、Co、Ni、Cu、Zn、V、Cr、Mn中的一 种或几种。结构上来看，钠过渡金属氧化物可以具有层状结构、隧道结构等。
“聚阴离子型化合物”指的是一系列含有四面体或八面体阴离子单元的一类化合物。按照阴离子的类型，其可以被划分为多种不同的体系。例如，磷酸盐体系、焦磷酸盐体系、氟代焦磷酸盐体系、硫酸盐体系、混合阴离子体系等。
在一个示例中，聚阴离子型化合物可以是具有钠离子、过渡金属离子以及四面体阴离子单元(YO4)d-的化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的一种或几种，Y可以是P、S及Si中的一种或几种，d表示(YO4)d-的价态。
在一个示例中，聚阴离子型化合物可以是具有钠离子、过渡金属离子、四面体阴离子单元(YO4)d-以及卤素阴离子的化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的一种或几种，Y可以是P、S及Si中的一种或几种，d表示(YO4)d-的价态，卤素可以是F、Cl及Br中的一种或几种。
在另一个示例中，聚阴离子型化合物还可以是具有钠离子、四面体阴离子单元(YO4)d-、多面体单元(ZOf)g+以及可选的卤素阴离子的化合物。Y可以是P、S及Si中的一种或几种，d表示(YO4)d-的价态，Z表示过渡金属，其可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的一种或几种，g表示(ZOf)g+的价态，卤素可以是F、Cl及Br中的一种或几种。
通常情况下，电池单体包括正极极片、负极极片、电解质和隔离件。在电池单体的充放电过程中，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。隔离件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，同时可以使活性离子通过。在一些实施例中，上述电池单体又称为二次电池。
与锂离子电池类似，钠离子电池依靠钠离子在正负极之间不断脱出、嵌入的电化学反应实现充放电。在钠离子电池的充电过程中，钠离子从正极活性材料中脱出，移动并嵌入到负极活性材料中，同时电子经外电路由正极流向负极；而放电过程中，钠离子从负极活性材料中脱出，移动并嵌入正极活性材料中，同时电子经外电路由负极流向正极。
应理解，本申请所述的“嵌入”过程指钠离子由于电化学反应在正极活 性材料和负极活性材料中嵌入的过程，本申请所述的“脱出”过程指钠离子由于电化学反应在正极活性材料和负极活性材料中脱出的过程。
钠金属电池是一类特殊的钠离子电池，钠金属电池中直接使用金属钠作为负极活性材料。传统的钠离子电池中，通常使用硬碳作为负极活性材料，该材料的理论容量较低。而钠金属具有1166mAh/g的理论容量，使得以钠金属作为负极的电池系统能够具有更高的能量密度。此外，与普通的钠离子电池相比，钠金属电池具有较高的电压，更长的循环寿命和更高的充放电速率，因此，钠金属电池成为极具发展潜力的新一代二次电池。
目前，对钠金属电池的研究集中于负极材料和电解质，正极活性材料通常直接挪用钠离子电池的正极活性材料。实际上，由于钠金属的高理论容量，钠离子电池中的正极活性材料通常无法提供相应的能量密度，限制了钠金属电池的容量，影响了钠金属电池的发展。
有鉴于此，本申请提供一种钠金属电池的正极活性材料，能够为钠金属电池贡献较高的能量密度，同时，帮助提高钠金属电池的容量和功率性能。
接下来，对钠金属电池中的电极材料、正极极片、负极极片、隔离件及电解质等部分进行详细介绍。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，正极膜层包括正极活性材料。
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，正极膜层可以设置在正极集流体相对的两个表面的其中任意一者或两者上。
可选地，正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，可采用铝箔。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层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、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。
本申请的实施例首先提供一种钠金属电池的正极活性材料，包括钠过渡金属氧化物和聚阴离子型化合物，其中，钠过渡金属氧化物的比表面积满足：0.4m2/g≤BET1≤4.0m2/g，聚阴离子型化合物的比表面积满足：10m2/g ≤BET2≤20m2/g。
具体来说，BET1可以为0.4m2/g、0.5m2/g、0.6m2/g、0.7m2/g、0.8m2/g、0.9m2/g、1.0m2/g、1.2m2/g、1.4m2/g、1.6m2/g、1.8m2/g、2.0m2/g、2.2m2/g、2.4m2/g、2.6m2/g、2.8m2/g、3.0m2/g、3.2m2/g、3.4m2/g、3.6m2/g、3.8m2/g、4.0m2/g或其数值范围在上述任意两个数值组合所获得的范围之内。BET2可以为10m2/g、11m2/g、12m2/g、13m2/g、14m2/g、15m2/g、16m2/g、17m2/g、18m2/g、19m2/g、20m2/g，或其数值范围在上述任意两个数值组合所获得的范围之内。
通常来说，钠过渡金属氧化物具有较高的容量，但单独作为正极活性材料的情况下，其结构稳定性较差，不利于电池的长循环。聚阴离子型化合物具有稳定的结构以及较高的工作电压，能够为电池提供较高的功率，但其单独作为正极活性材料的情况下，容量十分有限，无法实现钠金属电池对能量密度的需求。本实施例中，通过在聚阴离子型化合物中复配钠过渡金属氧化物作为正极活性材料，能够使钠金属电池兼具较高的容量和功率。并且，通过控制两种不同材料的比表面积在上述数值范围内，有助于提高复配后材料的粉末压实密度，从而在实现高容量、高功率的钠金属电池的同时，提高钠金属电池的能量密度。
可选地，正极活性材料在29400N压力下的粉末压实密度满足：1.8g/cm3≤ρ≤2.8g/cm3。
具体来说，正极活性材料在29400N压强下的粉末压实密度ρ可以是1.8g/cm3、1.9g/cm3、2.0g/cm3、2.1g/cm3、2.2g/cm3、2.3g/cm3、2.4g/cm3、2.5g/cm3、2.6g/cm3、2.7g/cm3、2.8g/cm3，或其数值范围在上述任意两个数值组合所获得的范围之内。
可选地，正极活性材料中，钠过渡金属氧化物的质量m1与聚阴离子型化合物的质量m2的比值满足：1/9≤m1/m2≤1。
具体来说，m1/m2可以是1/9、1/8、1/7、1/6、1/5、1/4、1/3、1/2、1，或其数值范围在上述任意两个数值组合所获得的范围之内。
可选地，钠过渡金属氧化物的质量m1与正极活性材料的质量m的比值满足：0.1≤m1/m≤0.5。
具体来说，m1/m可以是0.1、0.2、0.3、0.4、0.5，或其数值范围在上述 任意两个数值组合所获得的范围之内。
可选地，聚阴离子型化合物的质量m2与正极活性材料的质量m的比值满足：0.5≤m2/m≤0.9，且0＜(m1+m2)/m≤1。
具体来说，m2/m可以是0.5、0.6、0.7、0.8、0.9，或其数值范围在上述任意两个数值组合所获得的范围之内。
可选地，聚阴离子型化合物中的阴离子包括磷酸根、焦磷酸根、氟代焦磷酸根、硫酸根中的至少一种。
可选地，聚阴离子型化合物包括NaxM1yPmOn；其中，M1表示金属元素，金属元素包括Mn、Fe、Co、Cu、Al、Ti、V中的至少一种，1≤x≤2，0＜y≤1，0＜m≤2，4≤n≤8，且0＜x/m≤1。
可选地，钠过渡金属氧化物包括NaaM2bOc；其中，M2表示过渡金属元素，0.3≤a≤1.2，0≤b≤1，2≤c≤2.1。
可选地，过渡金属元素包括Ni、Mn、Fe、Co、Cu、Ti、Cr、V、Zn中的至少一种。
可选地，正极膜层还可选地包括粘结剂。作为示例，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-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
可选地，正极膜层包括导电剂。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、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如NMP)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片通常包括负极集流体，或包括负极集流体和设置在负极集流体至少一个表面上的负极膜层，负极膜层包括负极活性材料。
在一些实施方式中，钠金属电池的负极极片为负极集流体，即负极集流体直接作为负极极片，该类型的钠金属电池也可以称为“无负极电池”。在 充电过程中，依靠从正极极片脱出的钠离子沉积至负极集流体上形成钠金属负极，钠金属负极中，钠金属为负极活性材料。在另一些实施方式中，为了负极极片的正常使用，或便于钠金属在负极集流体上沉积，负极集流体上可以设置一层导电的膜层。
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，负极膜层可以设置在负极集流体相对的两个表面的其中任意一者或两者上。
可选地，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。
可选地，负极活性材料可以采用本领域公知的用于钠金属电池的负极活性材料。作为示例，负极活性材料可以包括以下材料中的至少一种：钠金属、沉积有钠金属的碳基材料或金属、合金材料、含有钠金属的复合材料、含有钠金属的合金材料等。但本申请并不限定于这些材料，还可以使用其他可被用作钠金属电池负极活性材料的其他材料。这些负极活性材料可以仅单独使用一种，也可以将两种或两种以上的材料组合使用。
可以按照本领域常规方法制备上述负极极片。例如，可以将铜箔或在铜箔的至少一个表面上设置有导电膜层的铜箔作为负极极片。导电膜层可以通过物理气相沉积(Physical Vapor Deposition,PVD)、旋涂、电镀、化学气相沉积(Chemical Vapor Deposition，CVD)等方法设置于负极集流体的至少一个表面。
[电解质]
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。
在一些实施方式中，电解质采用电解液。电解液包括电解质盐和溶剂。
可选地，电解质盐包括NaPF6、NaBCl4、NaSO3CF3及Na(CH3)C6H4SO3等。
可选地，溶剂包括碳酸酯或醚类溶剂。碳酸酯类溶剂包括环状的碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、氟代碳酸乙烯酯(FEC)以及链状的二甲基碳酸酯(DMC)、二乙基碳酸酯(DEC)、甲基乙基碳酸酯(EMC)等；醚类溶剂包括乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、四氢呋喃、1，3-二氧五环等。
可选地，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。
[隔离件]
在一些实施方式中，钠金属电池中还包括隔离件。本申请对隔离件的种类没有特别的限制，例如，隔离件可以是隔离膜。隔离膜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。
可选地，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。
本申请实施例还提供一种钠金属的电池单体，该电池单体包括本申请任一实施例中的正极极片。
在一些实施方式中，上述正极极片、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。
在一些实施方式中，电池单体可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，电池单体的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。电池单体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。
本申请对电池单体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1是作为一个示例的方形结构的钠金属电池的电池单体100。
图2是作为一个示例的钠金属电池的电池模块200。参照图2，在电池 模块200中，多个电池单体100可以是沿电池模块200的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个电池单体100进行固定。
可选地，在一个实施例中，电池模块200还可以包括具有容纳空间的外壳，多个电池单体100容纳于该容纳空间。
可选地，在一个实施例中，上述电池模块200还可以组装成钠金属电池，钠金属电池所含电池模块200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的应用和容量进行选择。
图3和图4是作为一个示例的钠金属电池300。参照图3和图4，在钠金属电池300中可以包括电池箱和设置于电池箱中的多个电池模块200。电池箱包括上箱体301和下箱体302，上箱体301能够盖设于下箱体302，并形成用于容纳电池模块200的封闭空间。多个电池模块200可以按照任意的方式排布于电池箱中。
应理解，在另一些实施例中，上述钠金属电池300又称作钠金属电池包。电池单体100可以先组成电池模块200，钠金属电池300由电池模块200组成。也可以直接由电池单体100组成钠金属电池300，省去电池模块200这一中间形态。
另外，本申请还提供一种用电装置，用电装置包括本申请提供的钠金属电池的电池单体100、钠金属电池的电池模块200、或钠金属电池300中的至少一种。电池单体100、电池模块200、或钠金属电池300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。
作为用电装置，可以根据其使用需求来选择电池单体100、电池模块200、或钠金属电池300的数量。
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，可以采用钠金属电池300或电池模块200。
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，可以采用电池单体100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1-11及对比例1-3]
实施例1
(1)正极极片的制备
将聚阴离子型化合物NaFePO4、钠过渡金属氧化物Na0.95Mn0.33Ni0.33Fe0.33O2、导电炭黑(Super P)、粘结剂PVDF按质量45:45:5:5比在适量的NMP中充分搅拌均匀，形成正极浆料，将正极浆料涂覆于正极集流体铝箔上，经过干燥、冷压后得到正极极片。
(2)负极极片的制备
将碳纳米管和海藻酸钠加入去离子水中搅拌形成均匀的浆料，将该浆料涂覆于铜箔上，经过干燥、冷压后得到“无负极”的负极极片。其中，涂层的面密度为20g/m2。
或者，进一步地，将上述经过干燥、冷压后的“无负极”极片进行裁剪，将该极片与正极极片、隔离膜组装成电池单体，将组装后的电池单体以0.5C恒流充电至3.8V，从而在该极片上预先沉积钠金属；在电池单体充满电后，于手套箱中拆出满充后的该极片，作为负极极片。
(3)电池单体的组装
将上述正极极片、玻纤薄膜以及负极极片按顺序叠放，经卷绕后形成电极组件，将电极组件装入包装外壳中，加入1M NaPF6电解液，经封装、化成、静置等工艺后，得到钠金属电池。其中，电解液的溶剂为二甲醚(Methoxymethane,DME)。
实施例1中，正极活性材料包括NaFePO4和Na0.95Mn0.33Ni0.33Fe0.33O2。其中，Na0.95Mn0.33Ni0.33Fe0.33O2的比表面积BET1＝0.4m2/g；NaFePO4的比表面积BET2＝10m2/g；Na0.95Mn0.33Ni0.33Fe0.33O2的质量m1与NaFePO4m2的质量m2的比值：m1/m2＝1/4；Na0.95Mn0.33Ni0.33Fe0.33O2的质量m1与正极活性材料的质量m的比值：m1/m＝1/5；NaFePO4的质量m2与正极活性材料的质量m的比 值：m2/m＝4/5；正极活性材料在29400N压力下的粉末压实密度ρ＝2.2g/cm3。
实施例2
与实施例1相比，实施例2的钠金属电池中，BET1＝4.0m2/g，BET2＝20m2/g，ρ＝1.9g/cm3。
实施例3
与实施例1相比，实施例3的钠金属电池中，BET1＝0.8m2/g，BET2＝12m2/g，m1/m2＝1，m1/m＝1/2，m2/m＝1/2，ρ＝2.5g/cm3。
实施例4
与实施例1相比，实施例4的钠金属电池中，BET1＝2m2/g，BET2＝10m2/g，ρ＝2.1g/cm3。
实施例5
与实施例1相比，实施例5的钠金属电池中，BET1＝2m2/g，BET2＝20m2/g，ρ＝1.9g/cm3。
实施例6
与实施例1相比，实施例6的钠金属电池中，m1/m2＝1/9，m1/m＝1/10，m2/m＝9/10，ρ＝2.1g/cm3。
实施例7
与实施例1相比，实施例7的钠金属电池中，m1/m2＝1，m1/m＝1/2，m2/m＝1/2，ρ＝2.6g/cm3。
实施例8
与实施例1相比，实施例8的钠金属电池中，正极活性材料还包括普鲁士蓝类化合物Na2Fe[Fe(CN)6]，其中，BET1＝0.4m2/g，BET2＝10m2/g，m1/m2＝1，m1/m＝2/7，m2/m＝2/7，Na2Fe[Fe(CN)6]的质量m3与正极活性材料的质量m的比值：m3/m＝3/7，ρ＝2.8g/cm3。
实施例9
与实施例1相比，实施例9的钠金属电池中，ρ＝1.8g/cm3。
实施例10
与实施例1相比，实施例10的钠金属电池中，ρ＝2.8g/cm3。
实施例11
与实施例1相比，实施例11的钠金属电池中，正极活性材料包括钠过 渡金属氧化物NaMn0.4Fe0.2Ni0.4O2和聚阴离子型化合物Na2FeP2O7。其中，NaMn0.4Fe0.2Ni0.4O2的比表面积BET1＝0.4m2/g；Na2FeP2O7的比表面积BET2＝10m2/g；NaMn0.4Fe0.2Ni0.4O2的质量m1与Na2FeP2O7的质量m2的比值：m1/m2＝1/4；Na2FeP2O7的质量m1与正极活性材料的质量m的比值：m1/m＝1/5；NaMn0.4Fe0.2Ni0.4O2的质量m2与正极活性材料的质量m的比值：m2/m＝4/5；正极活性材料在29400N压力下的粉末压实密度ρ＝2.7g/cm3。
对比例1
与实施例1相比，对比例1的钠金属电池中，正极活性材料仅包括NaFePO4，即m1/m＝1，ρ＝1.6g/cm3。
对比例2
与实施例1相比，BET1＝10m2/g，BET2＝30m2/g，ρ＝1.4g/cm3。
对比例3
与实施例1相比，BET1＝5m2/g，BET2＝30m2/g，ρ＝1.6g/cm3。
表1实施例及对比例的产品参数

表1中，BET1代表正极活性材料中钠过渡金属氧化物的比表面积，BET2代表正极活性材料中聚阴离子型化合物的比表面积，m1/m2代表正极材料中钠过渡金属氧化物的质量m1与聚阴离子型化合物的质量m2的比值，m1/m代表正极活性材料中钠过渡金属氧化物的质量m1与正极活性材料的质量m的比值，m2/m代表正极材料中聚阴离子型化合物的质量m2与正极活性材料的质量m的比值，ρ代表正极活性材料在29400N的压力下的粉末压实密度。
上述实施例1-11及对比例1-3的钠金属电池性能测试结果详见表2。
表2不同实施例及对比例电池性能测试结果

上述实施例1-11均展现出明显优于对比例1-3的能量密度。
通过实施例1和对比例1的性能对比可以看出，相比于单独使用聚阴离子型化合物作为正极活性材料，通过复合钠过渡金属氧化物和聚阴离子型化合物作为正极活性材料时，在相同的压力下，实施例1中正极活性材料的粉末压实密度相比于对比例1中正极活性材料的粉末压实密度显著增大，实施例1中钠金属电池的能量密度也明显高于对比例1。由此，说明通过复配钠过渡金属氧化物和聚阴离子型化合物两种材料，有助于提高单位面积的极片上能够负载的活性物质的量，从而提高了钠金属电池的能量密度。
通过实施例1和对比例2-3的性能对比可以看出，相比于实施例1，对比例2中钠过渡金属氧化物的比表面积为10m2/g，超出了0.4m2/g-4m2/g的范围；聚阴离子型化合物的比表面积为30m2/g，也超出了10m2/g-20m2/g的范围。可以看到，实施例1中正极活性材料的粉末压实密度明显高于对比例2-3的粉末压实密度，且实施例1中钠金属电池的能量密度也明显高于对比例2-3。由此，说明在复配钠过渡金属氧化物和聚阴离子型化合物的情况下，通过控制两种材料的比表面积分别在合适的范围内，才可以提升复配得到的正极活性材料的粉末压实密度，从而提升钠金属电池的能量密度。仅靠复配两种材料无法而不控制粉末压实密度在上述范围内，无法实现提升粉末压实密度和能量密度的效果。
进一步地，通过实施例1-5可以看到，控制钠过渡金属氧化物和聚阴 离子型化合物的比表面积分别在合适的范围内，均能够获得能量密度有所提升的钠金属电池。
通过实施例1、6-7可以看到，调整正极活性材料中过渡金属氧化物和聚阴离子型化合物的比例也能够影响钠离子电池能量密度。在其他条件相同的情况下，通过控制两种材料的比例相同(实施例7)可以获得最高的能量密度。
接下来，对本申请实施例涉及的物理参数、性能参数的测试方法进行介绍。
1.BET的测试方法
测试方法参考标准GB/T19587-2004《气体吸附BET法测定固态物质比表面积》。
取待测样品8g-15g装到样品管中，记录待测样品的初始质量。将称重的待测样品装入设备NOVA2000e中。然后开始脱气，并将待测样品加热至200℃后，保持2h。之后记录脱气后待测样品的质量。然后将脱气后的待测样品重新装入设备中，倒入液氮进行BET测试。设定氮气压力0.08MPa-0.12MPa，加热温度为40℃-350℃。测试结束后，从测试结果中读取比表面积。
2.粉末压实密度的测试方法
材料的粉末压实密度可以采用本领域已知的方法测试。例如可参照GB/T 24533-2009，使用电子压力试验机(如UTM7305)测试：将一定量的粉末放于压实专用模具上，设置不同压力，在设备上可以读出不同压力下粉末的厚度，计算可得不同压力下的压实密度。
3.电池能量密度的测试方法
在25℃、常压环境下，将钠金属电池以0.2C恒流充电至3.65V，然后以3.65V恒压充电至电流小于等于0.05C，然后静置5min，记录此时的充电容量，即首次充电容量；再以0.2C恒流放电至电压小于等于1.5V，记录此时的放电容量。能量密度＝放电容量/活性材料的质量。其中，活性材料指正极活性材料和负极活性材料。
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 (13)

  1. 一种钠金属电池的正极活性材料，其特征在于，所述正极活性材料包括：
    钠过渡金属氧化物和聚阴离子型化合物；
    其中，所述钠过渡金属氧化物的比表面积满足：0.4m2/g≤BET1≤4.0m2/g，所述聚阴离子型化合物的比表面积满足：10m2/g≤BET2≤20m2/g。
  2. 根据权利要求1所述的正极活性材料，其特征在于，所述正极活性材料在29400N压力下的粉末压实密度满足：1.2g/cm3≤ρ≤2.8g/cm3。
  3. 根据权利要求1或2所述的正极活性材料，其特征在于，所述正极活性材料中，所述钠过渡金属氧化物的质量m1与所述聚阴离子型化合物的质量m2的比值满足：1/9≤m1/m2≤1。
  4. 根据权利要求1-3中任一项所述的正极活性材料，其特征在于，所述钠过渡金属氧化物的质量m1与所述正极活性材料的质量m的比值满足：0.1≤m1/m≤0.5。
  5. 根据权利要求1-4中任一项所述的正极活性材料，其特征在于，所述聚阴离子型化合物的质量m2与所述正极活性材料的质量m的比值满足：0.5≤m2/m≤0.9，且0＜(m1+m2)/m≤1。
  6. 根据权利要求1-5中任一项所述的正极活性材料，其特征在于，所述聚阴离子型化合物中的阴离子包括磷酸根、焦磷酸根、氟代焦磷酸根、硫酸根中的至少一种。
  7. 根据权利要求6所述的正极活性材料，其特征在于，所述正极活性材料聚阴离子型化合物包括NaxM1yPmOn；其中，M1表示金属元素，所述金属元素包括Mn、Fe、Co、Cu、Al、Ti、V中的至少一种，1≤x≤2，0＜y≤1，0＜m≤2，4≤n≤8，且0＜x/m≤1。
  8. 根据权利要求1-7中任一项所述的正极活性材料，其特征在于，所述钠过渡金属氧化物包括NaaM2bOc；其中，M2表示过渡金属元素，0.3≤a≤1.2，0＜b≤1，2≤c≤2.1。
  9. 根据权利要求8所述的正极活性材料，其特征在于，所述过渡金属元素包括Ni、Mn、Fe、Co、Cu、Ti、Cr、V、Zn中的至少一种。
  10. 一种钠金属电池的正极极片，其特征在于，所述正极极片包括如权利要求1-9中任一项所述的正极活性材料。
  11. 一种钠金属电池的电池单体，其特征在于，所述电池单体包括如权利要求10所述的正极极片。
  12. 一种钠金属电池，其特征在于，所述钠金属电池包括如权利要求11所述的电池单体。
  13. 一种用电装置，其特征在于，所述用电装置包括如权利要求11所述的电池单体和/或如权利要求12所述的钠金属电池。
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