WO2025194875A1 - 补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备 - Google Patents

补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备

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Publication number
WO2025194875A1
WO2025194875A1 PCT/CN2024/138741 CN2024138741W WO2025194875A1 WO 2025194875 A1 WO2025194875 A1 WO 2025194875A1 CN 2024138741 W CN2024138741 W CN 2024138741W WO 2025194875 A1 WO2025194875 A1 WO 2025194875A1
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WO
WIPO (PCT)
Prior art keywords
sodium
supplementing
supplement
positive electrode
present application
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/138741
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English (en)
French (fr)
Inventor
涂龙
张国栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Hithium Energy Storage Technology Co Ltd
Original Assignee
Xiamen Hithium Energy Storage Technology Co Ltd
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Publication date
Application filed by Xiamen Hithium Energy Storage Technology Co Ltd filed Critical Xiamen Hithium Energy Storage Technology Co Ltd
Publication of WO2025194875A1 publication Critical patent/WO2025194875A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M4/362—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 electrochemical technology, and in particular to a sodium supplement material and a preparation method thereof, a positive electrode sheet, a sodium ion battery, a battery pack and an electrical device.
  • Sodium-ion batteries are expected to replace traditional lithium-ion batteries in the energy storage field due to their advantages such as low cost, abundant sodium resources and relatively high energy density.
  • Using a positive electrode sodium supplement to replenish sodium in the positive electrode can reduce the adverse effects of sodium loss on the electrochemical performance of sodium-ion batteries.
  • existing positive electrode sodium supplements still suffer from high oxidative decomposition potentials, which limits their actual sodium replenishment effect in sodium-ion batteries, and the performance of sodium-ion batteries needs to be improved.
  • the present application discloses a sodium supplement material and a preparation method thereof, a positive electrode sheet, a sodium ion battery, a battery pack and an electrical device to improve the performance of the sodium ion battery.
  • the present application provides a sodium-supplementing material, comprising a sodium - supplementing agent NaxCyOzHw and a metal oxide catalyst, where 1 ⁇ x ⁇ 3 , 1 ⁇ y ⁇ 6 , 1 ⁇ z ⁇ 7, and 0 ⁇ w ⁇ 5; a first EDS test is performed on any first region on the surface of the sodium-supplementing material, and the content of the metal element belonging to the metal oxide catalyst is measured to be C0 ; a second EDS test is performed on the first region after melting, and the content of the metal element belonging to the metal oxide catalyst is measured to be C1 , and C1 > C0 .
  • the present application provides a method for preparing the sodium supplement material as described in the first aspect, comprising the following steps:
  • the sodium supplement agent after the particle size control treatment is mixed with an alcohol-based solvent to obtain a dispersion, wherein the median particle size D50 of the sodium supplement agent after the particle size control treatment is 1 ⁇ m to 3 ⁇ m;
  • the mixture is calcined in a gas atmosphere at a calcination temperature of 300° C. to 500° C. and a calcination time of 1 hour to 6 hours to obtain the sodium supplement material.
  • the present application provides a positive electrode plate comprising a current collector and a positive electrode active material layer disposed on at least one surface of the current collector, wherein the positive electrode active material layer comprises the sodium-supplementing material as described in the first aspect, or comprises the sodium-supplementing material prepared by the preparation method as described in the second aspect.
  • the present application provides a sodium ion battery, comprising the positive electrode sheet described in the third aspect.
  • the present application provides a battery pack comprising a housing and at least one sodium-ion battery as described in the fourth aspect, wherein the sodium-ion battery is housed in the housing.
  • the present application provides an electrical device comprising the sodium ion battery described in the fourth aspect or the battery pack described in the fifth aspect.
  • the present application provides a sodium-supplementing material, a preparation method thereof, a positive electrode plate, and a sodium -ion battery.
  • the sodium-supplementing material comprises a sodium -supplementing agent (NaxCyOzHw ) and a metal oxide catalyst.
  • a first EDS (Energy Dispersive X-ray Spectroscopy) test is performed on any first region on the surface of the sodium-supplementing material, and the content of the metal element belonging to the metal oxide catalyst is measured to be C0 .
  • a second EDS test is performed on the first region after melting, and the content of the metal element belonging to the metal oxide catalyst is measured to be C1 , where C1 > C0 .
  • the sodium-supplementing material having the above characteristics facilitates electron transfer, resulting in a low oxidative decomposition potential of the sodium-supplementing material, thereby improving the first-cycle sodium-supplementing effect of the sodium-supplementing material and enhancing the energy density and cycle performance of the sodium-ion battery.
  • FIG1 is a schematic structural diagram of a household energy storage system according to an embodiment of the present application.
  • FIG2 is a schematic structural diagram of an energy storage system according to an embodiment of the present application.
  • FIG3 is a scanning electron microscope (SEM) image of the sodium supplement material prepared in Example 1;
  • FIG4 is a SEM image of the sodium supplement material prepared in Comparative Example 4.
  • FIG5 is a dQ/dV differential capacity curve diagram of the first button battery in the first cycle charging process of Example 1;
  • FIG6 is a dQ/dV differential capacity curve of the first button battery of Comparative Example 1 during the first cycle of charging;
  • FIG7 is a first cycle charge and discharge curve of the second button battery of Example 1;
  • FIG8 is a first cycle charge and discharge curve of the second button battery of Comparative Example 3.
  • 1-energy storage device 2-electric energy conversion device, 3-first user load, 4-second user load, 400-energy storage system, 410-high voltage cable, 420-first electric energy conversion device, 430-second electric energy conversion device.
  • the terms “installed,” “disposed,” “provided with,” “connected,” and “connected” should be interpreted broadly. For example, they can refer to fixed connections, removable connections, or integral structures; mechanical connections or electrical connections; direct connections, indirect connections through an intermediary, or internal communication between two devices, elements, or components. Those skilled in the art will understand the specific meanings of these terms in this application based on the specific circumstances.
  • first means two or more.
  • the present application provides a sodium-supplementing material, comprising a sodium - supplementing agent NaxCyOzHw and a metal oxide catalyst, wherein 1 ⁇ x ⁇ 3, 1 ⁇ y ⁇ 6 , 1 ⁇ z ⁇ 7 , and 0 ⁇ w ⁇ 5; a first EDS test is performed on any first region on the surface of the sodium-supplementing material, and the content of the metal element belonging to the metal oxide catalyst is measured to be C0 ; a second EDS test is performed on the first region after melting, and the content of the metal element belonging to the metal oxide catalyst is measured to be C1 , where C1 > C0 .
  • the sodium-supplementing material of the present application has the above-mentioned characteristics, indicating that after the sodium-supplementing material of the present application is melted, more exposed metal oxide catalyst becomes, indicating that the metal oxide catalyst in the sodium-supplementing material of the present application is effectively coated by the sodium-supplementing agent.
  • This coating structure facilitates electron transfer, resulting in a low oxidative decomposition potential of the sodium-supplementing material, thereby improving the first-cycle sodium-supplementing effect of the sodium-supplementing material.
  • the sodium-supplementing material of the present application can release additional sodium ions during the first cycle of charging of the sodium-ion battery, thereby compensating for the sodium ion loss caused by the formation of the SEI film at the negative electrode and other side reactions, thereby improving the energy density and cycle performance of the sodium-ion battery.
  • the first region can be any preselected region on the surface of the sodium-supplementing material.
  • the first region can be a rectangular region of 500 nm x 500 nm, or a circular region of 0.25 ⁇ m2 to 1 ⁇ m2.
  • the first region can be heat-treated for 5 to 10 minutes to melt the sodium-supplementing material in the first region, and then a second EDS test can be performed on the melted first region.
  • the present application does not particularly limit the heat treatment method, as long as the sodium-supplementing material can be melted.
  • the first region can be heat-treated using an SEM device at an accelerating voltage of 10 kV or 20 kV.
  • the EDS test can be used to quantitatively analyze the content of various elements in the sodium supplement material, such as the metal element content of the metal oxide catalyst.
  • the metal oxide catalyst is titanium dioxide ( TiO2 ).
  • the titanium content can be obtained after the first EDS test, recorded as C0
  • the titanium content can be obtained after the second EDS test, recorded as C1 .
  • the sodium-supplementing material comprises a composite structure of a sodium-supplementing agent coated with a metal oxide catalyst.
  • This composite structure facilitates electron transfer, resulting in a low oxidative decomposition potential for the sodium-supplementing material, thereby enhancing the sodium-supplementing effect of the sodium-supplementing material during the first cycle of charging. This allows for the release of additional sodium ions during the first cycle of charging a sodium-ion battery, thereby improving the energy density and cycle performance of the sodium-ion battery.
  • the oxidative decomposition potential of the sodium-supplementing material is E pa , satisfying 4.10 V ⁇ E pa ⁇ 4.20 V, for example, the oxidative decomposition potential is 4.10 V, 4.12 V, 4.14 V, 4.15 V, 4.16 V, or 4.20 V.
  • the sodium-supplementing material of the present application has a lower oxidative decomposition potential than existing sodium-supplementing materials, can improve the first-cycle sodium-supplementing effect, improve the first-cycle irreversible capacity loss of the sodium-ion battery, and thus improve the first-cycle coulombic efficiency of the sodium-ion battery.
  • the oxidative decomposition potential refers to the potential corresponding to the oxidative decomposition reaction of the sodium supplement material during the charging process.
  • the median particle size D50 of the sodium-supplementing material is between 0.8 ⁇ m and 2 ⁇ m, for example, D50 is 0.8 ⁇ m, 1 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m, or 2 ⁇ m.
  • D50 is 0.8 ⁇ m, 1 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m, or 2 ⁇ m.
  • the mass percentage of the sodium-supplementing agent is 70% to 95%, and the mass percentage of the metal oxide catalyst is 5% to 30%.
  • the mass percentage of the sodium-supplementing agent is 70%, 75%, 80%, 85%, 90% or 95%; the mass percentage of the metal oxide catalyst is 5%, 10%, 15%, 20%, 25% or 30%.
  • the mass ratio of the sodium-supplementing agent and the metal oxide catalyst in the sodium-supplementing material within the above range, wherein the content of the sodium-supplementing agent is higher than the content of the metal oxide catalyst, it is beneficial to form a composite structure in which the sodium-supplementing agent encapsulates the metal oxide catalyst.
  • the sodium supplement is selected from at least one of CH 3 COONa, C 6 H 5 Na 3 O 7 , Na 2 C 4 O 4 , Na 2 CO 3 , Na 2 C 2 O 4 and Na 2 C 6 O 6.
  • the above sodium supplement has the advantages of being environmentally friendly, widely available, safe and non-toxic.
  • the metal oxide catalyst is selected from at least one of titanium dioxide, ruthenium dioxide, manganese dioxide, molybdenum dioxide, cobalt trioxide, ferrous oxide, and tin dioxide. These metal oxides can act as electron acceptors to accept electrons, thereby facilitating the formation of a composite structure in which the sodium supplementer encapsulates the metal oxide catalyst.
  • the present application provides a method for preparing the sodium supplement material as described in the first aspect, comprising the following steps:
  • Preparation of a dispersion mixing the sodium supplement agent after particle size control with an alcohol-based solvent to obtain a dispersion, wherein the median particle size D50 of the sodium supplement agent after particle size control is 1 ⁇ m to 3 ⁇ m;
  • Preparation of the mixture adding the catalyst precursor to the dispersion, mixing, and drying to obtain a mixture;
  • Preparation of sodium-supplementing material calcining the mixture in a gas atmosphere at a calcination temperature of 300° C. to 500° C. for a calcination time of 1 h to 6 h to obtain the sodium-supplementing material.
  • the sodium supplement agent can be regulated by controlling the particle size of the sodium supplement agent to obtain a sodium supplement agent with the above-mentioned particle size range.
  • the inventors have found that as the particle size of the sodium supplement agent decreases, its specific surface area increases accordingly.
  • the dispersion formed after the catalyst precursor is dissolved in the alcohol-based solvent can be more evenly distributed on the surface of the sodium supplement agent; after further research, the inventors found that the uniformity of the mixing of the catalyst precursor and the sodium supplement agent will affect the uniformity of the coating structure of the sodium supplement material obtained after calcination.
  • the present application uses a sodium supplement agent after particle size regulation to prepare a sodium supplement material, which can make the coating structure of the sodium supplement material more uniform, thereby improving the catalytic efficiency of the metal oxide catalyst in the sodium supplement material and reducing the oxidative decomposition potential of the sodium supplement material.
  • step of preparing the mixture using a catalyst precursor instead of directly using a metal oxide catalyst can make the sodium supplement agent and the catalyst precursor mixed evenly at the nanoscale, which is beneficial to making the coating structure of the sodium supplement material more uniform.
  • the transition metal oxide produced by the thermal decomposition process of the metal alkoxide can be introduced into the sodium-supplementing agent, and the catalyst precursor undergoes a thermal decomposition reaction to form a transition metal oxide, and other components produced by the thermal decomposition (such as small organic molecules, carbon monoxide, carbon dioxide and water, etc.) are vaporized and discharged.
  • the sodium-supplementing agent melts at this temperature, and the metal oxide catalyst is uniformly dispersed in the molten sodium-supplementing agent, thereby achieving uniform coating of the metal oxide catalyst by the sodium-supplementing agent, thereby forming a composite structure of the sodium-supplementing agent-coated metal oxide catalyst that is conducive to electron transfer.
  • the calcined product can be crushed by a crusher and sieved to obtain the sodium-supplementing material in the desired particle size range.
  • the method for preparing the sodium supplement material further comprises:
  • the particle size distribution of the sodium supplement is regulated by recrystallization, ball milling, crushing or spray drying to obtain the sodium supplement after particle size regulation.
  • the present application can reduce the particle size of the sodium supplement agent by treatment methods such as recrystallization, ball milling, crushing or spray drying.
  • the inventors have found that the commercially available sodium supplement agent has the disadvantage of large particle size, and recrystallization can effectively reduce the particle size of the sodium supplement agent.
  • recrystallization when using recrystallization to control the particle size of the sodium supplement agent, the following steps can be followed:
  • the precipitate is filtered and washed with anhydrous ethanol, and then vacuum dried at 110° C. to 130° C. for 24 h to 36 h to obtain a recrystallized sodium-supplementing material. After sieving, a sodium-supplementing material with a desired particle size is obtained.
  • the catalyst precursor is selected from at least one of tetrabutyl titanate, manganese diethylhexanoate, iron diethylhexanoate, copper diethylhexanoate, cobalt 2-ethylhexanoate, nickel diethylhexanoate, and stannous diethylhexanoate.
  • the catalyst precursor contains a transition metal element or a post-transition metal element, and in subsequent preparation steps, the transition metal oxide produced during the thermal decomposition of the organometallic salt can be introduced into the sodium supplement, forming a composite structure of the sodium supplement coated with the metal oxide catalyst, which is conducive to electron transfer.
  • the alcohol-based solvent is selected from at least one of methanol, ethanol and ethylene glycol, which is conducive to the dissolution of the catalyst precursor.
  • the present application has no particular limitation on the gas atmosphere during calcination, as long as the purpose of the present application can be achieved.
  • the gas atmosphere includes any one of argon, nitrogen and air.
  • the preparation method of the sodium-supplementing material provided in the present application is based on calcining a sodium-supplementing agent after particle size control treatment and a catalyst precursor, which can make the coating structure of the sodium-supplementing material more uniform, which is conducive to obtaining a sodium-supplementing material with better sodium-supplementing performance.
  • the preparation method of the present application is simple, and the prepared sodium-supplementing material has excellent sodium-supplementing performance and low cost, thereby improving the energy density and cycle performance of sodium-ion batteries while reducing the production cost of sodium-ion batteries.
  • the present application also provides a positive electrode plate, comprising a current collector and a positive electrode active material layer arranged on at least one surface of the current collector, the positive electrode active material layer comprising the sodium-supplementing material described in any of the above embodiments, or comprising the sodium-supplementing material prepared by the preparation method described in any of the above embodiments.
  • the positive electrode active material layer of the present application can be arranged on one surface or both surfaces in the thickness direction of the positive electrode current collector.
  • the positive electrode active material layer is arranged on the surface of the positive electrode current collector, that is, the positive electrode active material layer can be arranged in a partial area of one surface of the positive electrode current collector, or it can be arranged in the entire area of one surface of the positive electrode current collector.
  • the present application has no special restrictions on the positive electrode current collector, as long as the purpose of the present application can be achieved, for example, it can include but is not limited to aluminum foil, aluminum alloy foil or composite current collector, etc.
  • the thickness of the positive electrode current collector there is no special restriction on the thickness of the positive electrode current collector, as long as the purpose of the present application can be achieved, for example, the thickness is 8 ⁇ m to 13 ⁇ m.
  • the thickness of the positive electrode active material layer of the present application can be 150 ⁇ m to 400 ⁇ m.
  • the positive electrode active material layer also includes a positive electrode active material.
  • the present application has no special restrictions on the positive electrode active material, as long as the purpose of the present application can be achieved.
  • it may include at least one of sodium nickel manganate, sodium nickel iron manganate, sodium ferric sulfate, sodium vanadium phosphate, sodium copper iron manganate, sodium ferric pyrophosphate and sodium ferric pyrophosphate.
  • the positive electrode active material layer may further include a positive electrode conductive agent.
  • a positive electrode conductive agent may include, but is not limited to, at least one of conductive carbon black (Super P), carbon nanotubes (CNTs), Ketjen black (KB), graphene, graphene oxide, and acetylene black.
  • the mass percentage of the conductive agent in the positive electrode active material layer is 10% to 40%.
  • the positive electrode active material layer may further include a positive electrode binder. This application does not particularly limit the positive electrode binder, as long as it can achieve the objectives of this application.
  • it may include, but is not limited to, at least one of fluorine-containing resin, polypropylene resin, fiber-type binder, rubber-type binder, polyimide-type binder, and polyvinylidene fluoride (PVDF).
  • fluorine-containing resin polypropylene resin
  • fiber-type binder fiber-type binder
  • rubber-type binder rubber-type binder
  • polyimide-type binder polyimide-type binder
  • PVDF polyvinylidene fluoride
  • the present application also provides a sodium ion battery, comprising the positive electrode sheet described in any of the above embodiments.
  • the sodium ion battery of the present application also includes a negative electrode plate, a separator and an electrolyte, wherein the separator is located between the positive electrode plate and the negative electrode plate to play an isolation role.
  • the negative electrode plate generally includes a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer can be arranged on the surface of the negative electrode current collector, that is, the negative electrode active material layer can be arranged in a partial area of one surface of the negative electrode current collector, or it can be arranged in the entire area of one surface of the negative electrode current collector.
  • the present application has no special restrictions on the negative electrode current collector, as long as the purpose of the present application can be achieved.
  • it can include but is not limited to copper foil, copper alloy foil, nickel foil or composite current collector, etc.
  • the thickness of the negative electrode current collector there is no special restriction on the thickness of the negative electrode current collector, as long as the purpose of the present application can be achieved, for example, the thickness is 4 ⁇ m to 12 ⁇ m.
  • the thickness of the negative electrode material layer of the present application can be 70 ⁇ m to 200 ⁇ m.
  • the negative electrode active material layer may further include a negative electrode binder.
  • the present application does not particularly limit the negative electrode binder, as long as it can achieve the purpose of the present application.
  • the negative electrode binder may include at least one of acrylate, polyamide, polyimide, polyamideimide, polyvinylidene fluoride, styrene-butadiene rubber, sodium alginate, polyvinyl alcohol, polytetrafluoroethylene, and sodium carboxymethyl cellulose.
  • the material of the separator can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
  • the separator 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 sodium ion battery of the present application also includes an electrolyte.
  • the present application does not particularly limit the electrolyte, and those skilled in the art can choose according to actual needs, as long as the purpose of the present application can be achieved.
  • at least one of ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl propionate (EP), propyl propionate (PP), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), vinylene carbonate (VC) or fluoroethylene carbonate (FEC) is mixed in a certain mass ratio or volume ratio to obtain a non-aqueous organic solvent, and then sodium salt is added to dissolve and mix evenly.
  • the present application does not limit the type of sodium salt, as long as the purpose of the present application can be achieved.
  • the sodium salt can include at least one of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate and sodium p-toluenesulfonate.
  • the present application does not particularly limit the concentration of the sodium salt in the electrolyte, as long as the purpose of the present application can be achieved.
  • the concentration of the sodium salt is 1.0 mol/L to 2.0 mol/L.
  • the sodium ion battery of the present application also includes a housing.
  • the present application does not particularly limit the housing, and those skilled in the art can select it according to actual needs, as long as it can achieve the purpose of the present application.
  • the housing may include an aluminum-plastic film.
  • the preparation method of the sodium ion battery includes but is not limited to the following steps: stacking the positive electrode sheet, the separator, and the negative electrode sheet in order, and performing operations such as winding and folding as needed to obtain a bare cell with a wound structure, placing the bare cell in a packaging bag, injecting an electrolyte into the packaging bag, and sealing the packaging bag to obtain a sodium ion battery.
  • the present application also provides a battery pack comprising a housing and at least one sodium-ion battery according to any of the above embodiments, wherein the sodium-ion battery is housed in the housing.
  • the battery pack having these two batteries has excellent performance, which is beneficial for the use of the battery pack.
  • the fixation and protection of the battery can be increased, thereby improving the service life of the battery pack.
  • the battery pack may contain one or more sodium-ion batteries.
  • the battery pack contains multiple sodium-ion batteries, the multiple sodium-ion batteries may be connected in at least one of parallel and series connection.
  • the present application also provides an electrical device, including a sodium ion battery or battery pack in any of the above embodiments, which is conducive to improving the product competitiveness and performance of the electrical device.
  • the electrical device includes an electrical device body, and the sodium ion battery or battery pack is used to power the electrical device body.
  • the electrical device body includes a positive electrode and a negative electrode, the positive electrode plate of the sodium ion battery or battery pack is used to electrically connect to the positive electrode of the electrical device body, and the negative electrode plate of the sodium ion battery or battery pack is used to electrically connect to the negative electrode of the electrical device body to power the electrical device.
  • the electrical equipment of the present application may include but is not limited to: containers, household energy storage systems, battery vehicles, electric vehicles, ships, spacecraft, electric toys and electric tools, etc., among which spacecraft include airplanes, rockets, space shuttles and spacecraft, etc., electric toys include fixed or mobile electric toys, specifically electric car toys, electric ship toys and electric airplane toys, etc., and electric tools include metal cutting power tools, grinding power tools, assembly power tools and railway power tools, specifically electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators and electric planers.
  • Figure 1 is a structural diagram of a household energy storage system of an implementation scheme of the present application.
  • the implementation scheme of Figure 1 of the present application is illustrated by taking the household energy storage scenario in user-side energy storage as an example.
  • the energy storage device of the present application is not limited to the household energy storage scenario.
  • the present application provides a household energy storage system, which includes an energy conversion device 2 (photovoltaic panels), a first user load 3 (street lights), a second user load 4 (such as household appliances such as air conditioners), and an energy storage device 1.
  • the energy storage device 1 is a small energy storage box that can be mounted on an outdoor wall. Specifically, the photovoltaic panels can convert solar energy into electrical energy during periods of low electricity prices. The energy storage device 1 is used to store this electrical energy and supply it to street lights and household appliances for use during peak electricity prices, or to provide power during power outages/blackouts.
  • FIG 2 is a structural diagram of an energy storage system 400 of an implementation scheme of the present application.
  • the implementation scheme of Figure 2 of the present application is illustrated by taking the shared energy storage scenario on the generation/distribution side as an example.
  • the energy storage device 1 of the present application is not limited to its generation/distribution side energy storage scenario.
  • the present application provides an energy storage system 400, which includes: a high-voltage cable 410, a first electric energy conversion device 420, a second electric energy conversion device 430 and the energy storage device 1 provided in the present application.
  • the first electric energy conversion device 420 and the second electric energy conversion device 430 are used to convert other forms of energy into electric energy, which is connected to the high-voltage cable 410 and supplied to the power distribution network for use.
  • the excess power is stored in the energy storage device 1, reducing the wind and solar power abandonment rates and improving the problem of new energy power generation and consumption.
  • the power grid issues an instruction to transmit the power stored in the energy storage device 1 in conjunction with the high-voltage cable 410 in a grid-connected mode to the power consumption side, providing peak shaving, frequency regulation, standby and other services for the power grid operation, giving full play to the peak shaving role of the power grid, promoting peak shaving and valley filling of the power grid, and alleviating the power supply pressure of the power grid.
  • the first electric energy conversion device 420 and the second electric energy conversion device 430 can convert at least one of solar energy, light energy, wind energy, thermal energy, tidal energy, biomass energy and mechanical energy into electric energy.
  • “multiple” refers to two or more.
  • An energy storage box may also be provided outside the energy storage device 1 to accommodate the energy storage device 1.
  • the energy storage device 1 may include, but is not limited to, a single cell, a battery module, a battery pack, a battery system, and the like.
  • the actual application form of the energy storage device 1 provided in the embodiments of this application may be, but is not limited to, the products listed, and may also be other application forms.
  • the embodiments of this application do not impose strict restrictions on the application form of the energy storage device 1.
  • the embodiments of this application only illustrate the energy storage device 1 as a multi-core battery.
  • the energy storage device 1 is a single cell, the energy storage device 1 may be at least one of a cylindrical battery, a prismatic battery, and the like.
  • the prepared sodium supplement material, the conductive agent Ketjen Black, and the binder PVDF were mixed in a mass ratio of 60:30:10, and N-methylpyrrolidone (NMP) was added as a solvent and stirred evenly to obtain a sodium supplement slurry with a solid content of 60%.
  • NMP N-methylpyrrolidone
  • the sodium supplement slurry was then evenly coated onto a 10 ⁇ m thick aluminum foil with a single-side coating thickness of 20 ⁇ m.
  • the foil was then vacuum-dried at 110°C for 12 hours to obtain a sodium supplement electrode.
  • the obtained sodium supplement electrode was cut into 14 ⁇ m diameter discs for later use.
  • the positive electrode active material Na4Fe3 ( PO4 ) 2 ( P2Oa ) ( NFPP), the prepared sodium supplement material, the conductive agent Ketjen Black, and the binder PVDF were mixed in a mass ratio of 70:10:10:10. NMP was then added and stirred to obtain a positive electrode slurry with a solid content of 60%. The positive electrode slurry was then evenly coated onto a 10 ⁇ m-thick aluminum foil to a thickness of 20 ⁇ m on one side. The NFPP positive electrode sheet was then vacuum-dried at 110°C for 12 hours to obtain the NFPP positive electrode sheet. The resulting NFPP positive electrode sheet was cut into 14 ⁇ m-diameter discs for later use.
  • ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • Sodium salt NaClO4 was then added and dissolved in the solvent. After mixing evenly, an electrolyte solution was obtained.
  • the molar concentration of NaClO4 in the electrolyte solution was 1 mol/L.
  • a glass fiber membrane with a thickness of 260 ⁇ m was selected as the diaphragm.
  • a circular sodium sheet with a diameter of 14 ⁇ m was used as the counter electrode.
  • the circular sodium supplement electrode, diaphragm and circular sodium sheet prepared above were stacked in order, so that the diaphragm was placed between the circular sodium supplement electrode and the circular sodium sheet to act as an isolate. Then the prepared electrolyte was injected to assemble the first button battery.
  • a circular sodium sheet with a diameter of 14 ⁇ m was used as the counter electrode.
  • the NFPP positive electrode sheet, diaphragm and circular sodium sheet prepared above were stacked in order, with the diaphragm placed between the NFPP positive electrode sheet and the circular sodium sheet to act as an isolate.
  • the prepared electrolyte was then injected to assemble the second button battery.
  • the preparation of the sodium supplement material was the same as in Example 1, except that the type of catalyst precursor was adjusted to adjust the type of metal oxide catalyst according to Table 1.
  • the catalyst precursor of Example 5 was cobalt 2-ethylhexanoate
  • the catalyst precursor of Example 6 was manganese diethylhexanoate
  • the catalyst precursor of Example 7 was stannous diethylhexanoate.
  • Example 1 Except that the calcination temperature was adjusted to 400° C. and the calcination time was adjusted to 3 h in the preparation of the sodium-supplementing material, the rest was the same as in Example 1.
  • Example 1 Except that the calcination temperature was adjusted to 500° C. and the calcination time was adjusted to 2 h in the preparation of the sodium-supplementing material, the rest was the same as in Example 1.
  • Example 1 The process is the same as that of Example 1 except that the recrystallized Na 2 C 4 O 4 prepared in Example 1 is directly used as the sodium supplement material.
  • the process was the same as that in Example 1 except that the commercially available sodium supplement Na 2 C 4 O 4 was directly used as the sodium supplement material.
  • Example 1 No sodium-supplementing material was prepared, that is, no first button cell was prepared, and the NFPP positive electrode sheet did not contain sodium-supplementing material, so that the prepared second button cell also did not contain sodium-supplementing material. Other aspects were the same as in Example 1.
  • the positive electrode active materials NFPP, Ketjen Black, and PVDF were mixed in a mass ratio of 80:10:10, and then NMP was added and stirred evenly to obtain a positive electrode slurry with a solid content of 60%.
  • the positive electrode slurry was then evenly coated on a 10 ⁇ m thick aluminum foil to a thickness of 20 ⁇ m on one side.
  • the NFPP positive electrode sheet was then vacuum dried at 110°C for 12 hours to obtain the NFPP positive electrode sheet.
  • the resulting NFPP positive electrode sheet was cut into 14 ⁇ m diameter discs for later use.
  • a focused electron beam from a SEM (model SU8010) was used to excite a selected area on the surface of the sodium-supplementing material, generating secondary electrons, backscattered electrons, and characteristic X-rays. This secondary information was then collected and detected for quantitative composition analysis. Specifically, a random 500 nm x 500 nm rectangular area on the surface of the sodium-supplementing material was selected as the first area. A first EDS analysis was performed on this area to determine the content of the metal element associated with the metal oxide catalyst, denoted as C 0 . This first area was then heat-treated at an accelerating voltage of 10 kV for 5 minutes using the SEM to melt the sodium-supplementing material. A second EDS analysis was performed on the melted first area to determine the content of the metal element associated with the metal oxide catalyst, denoted as C 1 .
  • the first button cell was subjected to the first cycle charge and discharge test using the LAND test system to obtain a dQ/dV curve.
  • the oxidation peak of the dQ/dV curve corresponds to the oxidative decomposition reaction of the sodium-supplementing material, and the potential corresponding to the oxidation peak of the dQ/dV curve is the oxidative decomposition potential of the sodium-supplementing material.
  • the average particle size D50 of the sodium supplement material was tested using a laser particle size analyzer.
  • the test temperature is 25°C.
  • Table 1 Data of sodium supplement materials in various embodiments and comparative examples In Table 1, “/” indicates that there are no relevant preparation parameters.
  • Example 1 and Comparative Examples 1 and 2 show that when a commercially available sodium supplement is simply recrystallized (e.g., Comparative Example 1) or directly used as a sodium supplement material (e.g., Comparative Example 2), the sodium supplement materials in Comparative Examples 1 and 2 do not contain a metal oxide catalyst. Therefore, after two EDS tests, the metal elements of the metal oxide catalyst are absent. This also indicates that the sodium supplement materials in Comparative Examples 1 and 2 do not possess a composite structure of a sodium supplement coated with a metal oxide catalyst. Furthermore, the sodium supplement materials in Comparative Examples 1 and 2 have high oxidative decomposition potentials, resulting in low first-cycle charge capacities in the first button cell, making it difficult to improve the sodium supplement material's initial sodium supplement efficiency.
  • Example 1 and Comparative Example 4 when a commercially available sodium supplement is simply physically mixed with a commercially available TiO2 catalyst and used as the sodium supplement material, after two EDS tests, C1 ⁇ C0 , indicating that the sodium supplement material in Comparative Example 4 also does not possess a composite structure of a sodium supplement coated with a metal oxide catalyst. Furthermore, the sodium-supplementing material in Comparative Example 4 had a high oxidative decomposition potential, resulting in a low first-cycle charge capacity of the first button cell. Therefore, it was difficult to improve the sodium-supplementing effect of the sodium-supplementing material in the first cycle.
  • the sodium-supplementing material of the present application showed C 1 > C 0 , indicating that the sodium-supplementing material has a composite structure of a sodium-supplementing agent coated with a metal oxide catalyst, resulting in a low oxidative decomposition potential.
  • the first-cycle charge capacity of the first button cell was significantly improved, thereby enhancing the sodium-supplementing effect of the sodium-supplementing material in the first cycle.
  • FIG3 is an SEM image of the sodium supplement material prepared in Example 1. As can be seen from FIG3 , there are no obvious TiO 2 particles on the surface of the sodium supplement agent Na 2 C 4 O 4 , which also confirms that the sodium supplement material of the present application has a composite structure of a sodium supplement agent coated with a metal oxide catalyst.
  • FIG4 is a SEM image of the sodium supplement material prepared in Comparative Example 4. It can be seen from FIG4 that the TiO2 particles are only dispersed on the surface of the sodium supplement agent Na2C4O4 , and no composite structure of the sodium supplement agent coating the metal oxide catalyst is formed.
  • the type and content of the sodium supplement agent and metal oxide catalyst, as well as the particle size of the sodium supplement material, also affect the performance of the sodium ion battery. As can be seen from Examples 2 to 10, under the premise of C 1 > C 0 , by regulating the type and content of the sodium supplement agent and metal oxide catalyst, as well as the particle size of the sodium supplement material within the range of this application, a sodium ion battery with a high first-cycle charge capacity can be obtained.
  • Calcination time and temperature also affect the performance of sodium ion batteries. From Examples 11 and 12, it can be seen that, under the premise of C 1 > C 0 , by regulating the calcination time and temperature within the scope of this application, a sodium ion battery with a high first-cycle charge capacity can be obtained.
  • Example 1 and Comparative Examples 1 to Comparative Examples 4 it can be seen from Example 1 and Comparative Examples 1 to Comparative Examples 4 that when the commercially available sodium supplement is simply recrystallized (for example, Comparative Example 1), or the commercially available sodium supplement is directly used as the sodium supplement material (for example, Comparative Example 2), or the positive electrode sheet does not contain the sodium supplement material (for example, Comparative Example 3), or the commercially available sodium supplement is physically mixed with the commercially available TiO2 catalyst as the sodium supplement material (for example, Comparative Example 4), since the sodium supplement materials of Comparative Examples 1, 2, and 4 do not have a composite structure of a sodium supplement coated with a metal oxide catalyst, and the positive electrode sheet of Comparative Example 3 does not contain a sodium supplement material, the first-cycle charge capacity and the first-cycle discharge capacity of the second button battery are both low, resulting in a low first-cycle coulomb efficiency, which is not conducive to improving the energy density and cycle performance of the sodium ion battery; while the first-cycle charge capacity, the first-cycle discharge capacity,
  • the type and content of the sodium supplement agent and metal oxide catalyst, as well as the particle size of the sodium supplement material also affect the performance of the sodium ion battery.
  • Examples 2 to 10 under the premise of C 1 > C 0 , by regulating the type and content of the sodium supplement agent and metal oxide catalyst, as well as the particle size of the sodium supplement material within the scope of this application, it is advantageous to obtain a NFPP sodium ion battery with high first-cycle charge capacity, high first-cycle discharge capacity, and excellent cycle performance.
  • Calcination time and temperature also affect the performance of sodium-ion batteries. As can be seen from Examples 11 and 12, under the premise of C 1 > C 0 , by regulating the calcination time and temperature within the scope of this application, it is beneficial to obtain NFPP sodium-ion batteries with high first-cycle charge capacity, high first-cycle discharge capacity, and excellent cycle performance.
  • Figure 5 is a graph showing the dQ/dV differential capacity curve during the first charge cycle of the first button-type battery of Example 1
  • Figure 6 is a graph showing the dQ/dV differential capacity curve during the first charge cycle of the first button-type battery of Comparative Example 1.
  • the oxidation peak potential of Example 1 is 4.12V
  • the oxidation peak potential of Comparative Example 1 is 4.25V, indicating that the sodium-supplementing material of the present application has a lower oxidative decomposition potential, which is beneficial for improving the sodium-supplementing effect during the first charge cycle.
  • Figure 7 is the first cycle charge and discharge curve of the second button battery of Example 1;
  • Figure 8 is the first cycle charge and discharge curve of the second button battery of Comparative Example 3.
  • the first cycle charge capacity of the second button battery of Example 1 is increased to 138.4 mAh/g, and an oxidation platform is shown at about 4.12V.
  • the capacity provided by this part of the platform corresponds to the oxidative decomposition process of the sodium supplement material;
  • the first cycle charge capacity of Comparative Example 3 is 115.7 mAh/g, and its first cycle charge platform shows oxidation platforms at about 2.8V, 2.95V and 3.28V, corresponding to the Na3 site, Na1 site and Na4 site Na release process.
  • the first cycle discharge specific capacity of Example 1 is 105.1 mAh/g
  • the first cycle discharge specific capacity of Comparative Example 3 is 101.5 mAh/g
  • the capacity retention rate after 20 cycles of Example 1 is also improved compared with Comparative Example 1, which shows that the addition of the sodium supplement material of the present application will not affect the structure of the NFPP positive electrode sheet in the subsequent cycle process, and even plays a positive role.
  • the sodium-supplementing material of the present application can effectively compensate for the first-cycle sodium loss of the NFPP positive electrode sheet, showing good compatibility with the NFPP positive electrode sheet, which is beneficial to the improvement of the energy density and cycle performance of sodium-ion batteries.

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Abstract

本申请涉及电化学技术领域，具体公开了一种补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备，其中补钠材料包括补钠剂NaxCyOzHw和金属氧化物催化剂，1≤x≤3，1≤y≤6，1≤z≤7，0≤w≤5；对补钠材料表面的任意第一区域进行第一次EDS测试，测得属于金属氧化物催化剂的金属元素的含量为C0，对熔融后的第一区域进行第二次EDS测试，测得属于金属氧化物催化剂的金属元素的含量为C1，C1＞C0。

Description

补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备
优先权信息
本申请请求于2024年03月18日向中国国家知识产权局提交的、专利申请号为202410308708.7、申请名称为“补钠材料及其制备方法、正极极片、钠离子电池”的中国专利申请的优先权和权益，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及电化学技术领域，尤其涉及一种补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备。
背景技术
钠离子电池凭借低成本、钠资源丰富、能量密度相对较高等优点，有望在储能领域替代传统的锂离子电池。
通过正极补钠剂对正极极片进行补钠，能够减小因钠损耗而给钠离子电池的电化学性能带来的不利影响。但是现有的正极补钠剂仍存在高氧化分解电位的问题，限制了正极补钠剂在钠离子电池中的实际补钠效果，钠离子电池的性能有待提高。
发明内容
为了解决上述技术问题，本申请公开了一种补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备，以提高钠离子电池的性能。
第一个方面，本申请提供了一种补钠材料，包括补钠剂NaxCyOzHw和金属氧化物催化剂，1≤x≤3，1≤y≤6，1≤z≤7，0≤w≤5；对所述补钠材料表面的任意第一区域进行第一次EDS测试，测得属于所述金属氧化物催化剂的金属元素的含量为C0，对熔融后的所述第一区域进行第二次EDS测试，测得属于所述金属氧化物催化剂的金属元素的含量为C1，C1＞C0。
第二个方面，本申请提供一种如第一个方面所述的补钠材料的制备方法，包括以下步骤：
将经粒径调控处理后的补钠剂与醇基溶剂混合，得到分散液，其中，经粒径调控处理后的所述补钠剂的中值粒径D50为1μm～3μm；
将催化剂前驱体加入到所述分散液中进行混合，干燥后得到混合物；
将所述混合物在气体气氛下进行煅烧，煅烧温度为300℃～500℃，煅烧时间为1h～6h，得到所述补钠材料。
第三个方面，本申请提供一种正极极片，包括集流体和设置于所述集流体至少一个表面的正极活性材料层，所述正极活性材料层包括如第一方面所述的补钠材料，或者包括如第二方面所述的制备方法制得的补钠材料。
第四个方面，本申请提供一种钠离子电池，所述钠离子电池包括第三方面所述的正极极片。
第五个方面，本申请提供一种电池包，包括箱体和至少一个第四方面所述的钠离子电池，所述钠离子电池收容于所述箱体中。
第六个方面，本申请提供一种用电设备，包括第四方面所述的钠离子电池或第五方面所述的电池包。
与现有技术相比，本申请至少具有如下有益效果：
本申请提供了一种补钠材料及其制备方法、正极极片、钠离子电池，其中，补钠材料包括补钠剂NaxCyOzHw和金属氧化物催化剂，对补钠材料表面的任意第一区域进行第一次EDS(Energy Dispersive X-ray Spectroscopy，能量色散X射线光谱)测试，测得属于金属氧化物催化剂的金属元素的含量为C0，对熔融后的第一区域进行第二次EDS测试，测得属于金属氧化物催化剂的金属元素的含量为C1，C1＞C0。具有上述特征的补钠材料有利于电子转移，使得补钠材料具有低氧化分解电位，从而提高补钠材料的首圈补钠效果，提高钠离子电池的能量密度和循环性能。
附图说明
为了更清楚地说明本申请实施方案中的技术方案，下面将对实施方案中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施方案，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，还可以根据这些附图获得其他的附图。
图1为本申请一种实施方案的户用储能系统的结构示意图；
图2为本申请一种实施方案的储能系统的结构示意图；
图3为实施例1制得的补钠材料的扫描电子显微镜(SEM)图；
图4为对比例4制得的补钠材料的SEM图；
图5为实施例1的第一扣式电池的首圈充电过程的dQ/dV微分容量曲线图；
图6为对比例1的第一扣式电池的首圈充电过程的dQ/dV微分容量曲线图；
图7为实施例1的第二扣式电池的首圈充放电曲线；
图8为对比例3的第二扣式电池的首圈充放电曲线。
附图标记说明：1-储能装置，2-电能转换装置，3-第一用户负载，4-第二用户负载，400-储能系统，410-高压电缆，420-第一电能转换装置，430-第二电能转换装置。
具体实施方式
下面将结合本申请实施方案中的附图，对本申请实施方案中的技术方案进行清楚、完整地描述，显然，所描述的实施方案仅是本申请一部分实施方案，而不是全部的实施方案。基于本申请中的实施方案，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方案，都属于本申请保护的范围。
在本申请中，术语“上”、“下”、“左”、“右”、“前”、“后”、“顶”、“底”、“内”、“外”、“竖直”、“水平”、“横向”、“纵向”等指示的方位或位置关系为基于附图所示的方位或位置关系。这些术语主要是为了更好地描述本申请及其实施方案，并非用于限定所指示的装置、元件或组成部分必须具有特定方位，或以特定方位进行构造和操作。
并且，上述部分术语除了可以用于表示方位或位置关系以外，还可能用于表示其他含义，例如术语“上”在某些情况下也可能用于表示某种依附关系或连接关系。对于本领域普通技术人员而言，可以根据具体情况理解这些术语在本申请中的具体含义。
此外，术语“安装”、“设置”、“设有”、“连接”、“相连”应做广义理解。例如，可以是固定连接，可拆卸连接，或整体式构造；可以是机械连接，或电连接；可以是直接相连，或者是通过中间媒介间接相连，又或者是两个装置、元件或组成部分之间内部的连通。对于本领域普通技术人员而言，可以根据具体情况理解上述术语在本申请中的具体含义。
此外，术语“第一”、“第二”等主要是用于区分不同的装置、元件或组成部分(具体的种类和构造可能相同也可能不同)，并非用于表明或暗示所指示装置、元件或组成部分的相对重要性和数量。除非另有说明，“多个”的含义为两个或两个以上。
本申请提供一种补钠材料，该补钠材料包括补钠剂NaxCyOzHw和金属氧化物催化剂，其中，1≤x≤3，1≤y≤6，1≤z≤7，0≤w≤5；对补钠材料表面的任意第一区域进行第一次EDS测试，测得属于金属氧化物催化剂的金属元素的含量为C0，对熔融后的第一区域进行第二次EDS测试，测得属于金属氧化物催化剂的金属元素的含量为C1，C1＞C0。本申请的补钠材料具有上述特征，表明本申请的补钠材料熔融后，裸露的金属氧化物催化剂变得更多，这表明本申请补钠材料中的金属氧化物催化剂被补钠剂有效包覆，这种包覆结构从而有利于电子转移，使得补钠材料具有低氧化分解电位，从而提高补钠材料的首圈补钠效果。本申请的补钠材料能够在钠离子电池首圈充电过程中释放出额外的钠离子，从而补偿由于负极极片处SEI膜形成和其他副反应等原因导致的钠离子损耗，提高钠离子电池的能量密度和循环性能。
本申请中，第一区域可以是补钠材料表面的任意一个预先选定区域，例如，第一区域可以是一个500nm×500nm的矩形区域，或者是一个面积为0.25μm2～1μm2的圆形区域。在进行第一次EDS测试后，可以对第一区域进行热处理5min～10min，使第一区域的补钠材料熔融，然后对熔融后的第一区域进行第二次EDS测试。本申请对热处理方法没有特别限制，只要能使补钠材料熔融即可，示例性地，可以通过SEM装置在10kV或20kV加速电压下对第一区域进行热处理。
可以理解的是，通过EDS测试可以定量分析补钠材料中各元素的含量，例如金属氧化物催化剂的金属元素含量。在一种示例中，金属氧化物催化剂为二氧化钛(TiO2)，则可以在第一次EDS测试后得到钛元素的含量，记为C0，在第二次EDS测试后得到钛元素的含量，记为C1。
在本申请的一些实施方案中，补钠材料具有补钠剂包覆金属氧化物催化剂的复合结构。具有该复合结构的补钠材料有利于电子转移，使得补钠材料具有低氧化分解电位，从而提高补钠材料的首圈补钠效果，能够在钠离子电池首圈充电过程中释放出额外的钠离子，提高钠离子电池的能量密度和循环性能。
在本申请的一些实施方案中，补钠材料的氧化分解电位为Epa，满足4.10V≤Epa≤4.20V，例如，氧化分解电位为4.10V、4.12V、4.14V、4.15V、4.16V或4.20V。本申请的补钠材料相比于现有的补钠材料具有更低的氧化分解电位，能够提高首圈补钠效果，改善钠离子电池的首圈不可逆容量损失，从而提高钠离子电池的首圈库伦效率。
本申请中，氧化分解电位是指补钠材料在充电过程中发生氧化分解反应时对应的电位。
在本申请的一些实施方案中，补钠材料的中值粒径D50为0.8μm～2μm，例如，D50为0.8μm、1μm、1.2μm、1.5μm、1.8μm或2μm。通过调控补钠材料的D50在上述范围内，能够有效缩短电子在补钠材料颗粒之间的传输距离，从而促进补钠剂的氧化分解过程，有利于补钠材料氧化分解电位的降低。
在本申请的一些实施方案中，基于补钠材料的总质量为100％，补钠剂的质量百分含量为70％～95％，金属氧化物催化剂的质量百分含量为5％～30％。例如，补钠剂的质量百分含量为70％、75％、80％、85％、90％或95％；金属氧化物催化剂的质量百分含量为5％、10％、15％、20％、25％或30％。通过调控补钠材料中补钠剂和金属氧化物催化剂的质量比在上述范围内，其中的补钠剂含量高于金属氧化物催化剂的含量，有利于形成补钠剂包覆金属氧化物催化剂的复合结构。
在本申请的一些实施方案中，补钠剂选自CH3COONa、C6H5Na3O7、Na2C4O4、Na2CO3、Na2C2O4和Na2C6O6中的至少一种。上述补钠剂具有环境友好、来源广泛、安全无毒的优点。
在本申请的一些实施方案中，金属氧化物催化剂选自二氧化钛、二氧化钌、二氧化锰、二氧化钼、四氧化三钴、四氧化三铁和二氧化锡中的至少一种。上述金属氧化物可以作为电子受体接受电子，有利于形成补钠剂包覆金属氧化物催化剂的复合结构。
第二个方面，本申请提供一种如第一个方面所述的补钠材料的制备方法，包括以下步骤：
分散液的制备：将经粒径调控处理后的补钠剂与醇基溶剂混合，得到分散液，其中，经粒径调控处理后的补钠剂的中值粒径D50为1μm～3μm；
混合物的制备：将催化剂前驱体加入到分散液中进行混合，干燥后得到混合物；
补钠材料的制备：将混合物在气体气氛下进行煅烧，煅烧温度为300℃～500℃，煅烧时间为1h～6h，得到补钠材料。
在分散液的制备步骤中，可以通过对补钠剂进行粒径调控从而得到上述粒径范围的补钠剂。发明人研究发现，随着补钠剂粒径的减小，其比表面积随之增大，在后续混合物的制备过程中，催化剂前驱体溶于醇基溶剂后形成的分散液能够更加均匀地分布在补钠剂的表面；发明人进一步研究后发现，催化剂前驱体与补钠剂混合的均匀程度会影响煅烧后所得补钠材料包覆结构的均匀程度。基于此，本申请采用经粒径调控后的补钠剂来制备补钠材料，能够使补钠材料的包覆结构更加均匀，从而提高补钠材料中金属氧化物催化剂的催化效率，降低补钠材料的氧化分解电位。
在混合物的制备步骤中，使用催化剂前驱体而非直接使用金属氧化物催化剂，能够使补钠剂与催化剂前驱体在纳米尺度上混合均匀，有利于使补钠材料的包覆结构更加均匀。
在补钠材料的制备步骤中，通过本申请的煅烧工艺，也即，调控煅烧温度和煅烧时间在上述范围内，能够将金属醇盐热分解过程产生的过渡金属氧化物引入到补钠剂中，同时催化剂前驱体发生热分解反应形成过渡金属氧化物，热分解产生的其它组分(例如有机小分子、一氧化碳、二氧化碳和水等)汽化排出，并且，补钠剂在该温度下发生熔融，金属氧化物催化剂均匀分散在熔融的补钠剂中，实现补钠剂对金属氧化物催化剂的均匀包覆，从而形成有利于电子转移的补钠剂包覆金属氧化物催化剂的复合结构。
在补钠材料的制备步骤中，可以将煅烧后所得产物通过破碎机进行破碎处理，过筛后得到所需粒径范围的补钠材料。
在本申请的一些实施方案中，补钠材料的制备方法还包括：
通过再结晶处理、球磨处理、破碎处理或者喷雾干燥处理来调控补钠剂的粒径分布，得到粒径调控处理后的补钠剂。
本申请可以通过再结晶处理、球磨处理、破碎处理或者喷雾干燥处理等处理方法减小补钠剂的粒径。发明人研究发现，市售补钠剂存在粒径较大的不足，再结晶处理能够有效减小补钠剂的粒径。示例性地，当采用再结晶处理来调控补钠剂粒径时，可以按照如下步骤进行：
将市售补钠剂粉末加入到去离子水中，搅拌后使补钠剂完全溶解，得到接近饱和的补钠剂溶液；
向补钠剂溶液中加入无水乙醇，搅拌后生成沉淀；
对沉淀采用无水乙醇进行抽滤、洗涤，然后在110℃～130℃条件下真空干燥24h～36h，得到再结晶的补钠材料，过筛后，得到所需粒径的补钠材料。
在本申请的一些实施方案中，催化剂前驱体选自钛酸四丁酯、二乙基己酸锰、二乙基己酸铁、二乙基己酸铜、2-乙基己酸钴、二乙基己酸镍和二乙基己酸亚锡中的至少一种。上述催化剂前驱体含有过渡金属元素或后过渡金属元素，能够在后续制备步骤中将有机金属盐热分解过程产生的过渡金属氧化物引入到补钠剂中，形成有利于电子转移的补钠剂包覆金属氧化物催化剂的复合结构。
在本申请的一些实施方案中，醇基溶剂选自甲醇、乙醇和乙二醇中的至少一种，有利于催化剂前驱体的溶解。
本申请对煅烧时的气体气氛没有特别限制，只要能实现本申请目的即可。在本申请的一些实施方案中，气体气氛包括氩气、氮气和空气中的任一种。
本申请提供的补钠材料的制备方法，基于经粒径调控处理后的补钠剂与催化剂前驱体进行煅烧制备，能够使补钠材料的包覆结构更加均匀，有利于得到补钠性能更好的补钠材料；并且，本申请的制备方法工艺简单，所制备的补钠材料具有优异的补钠性能和较低的成本，从而在提高钠离子电池的能量密度和循环性能的同时，降低钠离子电池的生产成本。
本申请还提供了一种正极极片，包括集流体和设置于集流体至少一个表面的正极活性材料层，正极活性材料层包括上述任一实施方案所述的补钠材料，或者包括上述任一实施方案所述的制备方法制得的补钠材料。
本申请的正极活性材料层可以设置于正极集流体厚度方向的一个表面或两个表面上。本申请中正极活性材料层设置在正极集流体的表面，即正极活性材料层可以设置在正极集流体一个表面的部分区域，也可以设置在正极集流体一个表面的全部区域。本申请对正极集流体没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于铝箔、铝合金箔或复合集流体等。在本申请中，对正极集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为8μm至13μm。本申请的正极活性材料层的厚度可以为150μm至400μm。
在本申请中，正极活性材料层中还包括正极活性材料，本申请对正极活性材料没有特别限制，只要能够实现本申请目的即可，例如可以包括镍锰酸钠、镍铁锰酸钠、硫酸铁纳、磷酸钒钠、铜铁锰酸钠、焦磷酸铁钠和焦磷酸铁钠中的至少一种。
在本申请中，正极活性材料层中还可以包括正极导电剂，本申请对正极导电剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于导导电炭黑(Super P)、碳纳米管(CNT)、科琴黑(KB)、石墨烯、氧化石墨烯和乙炔黑中的至少一种。导电剂在正极活性材料层中的质量百分含量为10％～40％。在本申请中，正极活性材料层还可以包括正极粘结剂，本申请对正极粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于含氟树脂、聚丙烯树脂、纤维型粘结剂、橡胶型粘结剂、聚酰亚胺型粘结剂和聚偏氟乙烯(PVDF)中的至少一种。
本申请还提供了一种钠离子电池，包括上述任一实施方案所述的正极极片。
本申请的钠离子电池中还包括负极极片、隔膜和电解液，其中，隔膜处于正极极片和负极极片之间，起到隔离作用。
本申请对负极极片没有特别限制，只要能实现本申请的目的即可，例如负极极片通常包括负极集流体和负极活性材料层。负极活性材料层可以设置在负极集流体的表面，即负极活性材料层可以设置在负极集流体一个表面的部分区域，也可以设置在负极集流体一个表面的全部区域。本申请对负极集流体没有特别限制，只要能够实现本申请目的即可，例如，可以包括但不限于铜箔、铜合金箔、镍箔或复合集流体等。在本申请中，对负极集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为4μm至12μm。本申请的负极材料层的厚度可以为70μm至200μm。
在本申请中，负极活性材料层中还可以包括负极粘结剂。本申请对负极粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括丙烯酸酯、聚酰胺、聚酰亚胺、聚酰胺酰亚胺、聚偏氟乙烯、丁苯橡胶、海藻酸钠、聚乙烯醇、聚四氟乙烯、羧甲基纤维素钠中的至少一种。
在一些实施方式中，隔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。
本申请的钠离子电池还包括电解液。本申请对电解液没有特别限制，本领域技术人员可以根据实际需要选择，只要能够实现本申请目的即可。例如，将碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸二乙酯(DEC)、丙酸乙酯(EP)、丙酸丙酯(PP)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸亚乙烯酯(VC)或碳酸氟代亚乙酯(FEC)等中的至少一种按照一定质量比例或体积比例混合得到非水有机溶剂后，加入钠盐溶解并混合均匀即可。本申请对钠盐的种类没有限制，只要能够实现本申请目的即可。例如，钠盐可以包括六氟磷酸钠、高氯酸钠、四氟硼酸钠、三氟甲基磺酸钠和对甲苯磺酸钠中的至少一种。本申请对钠盐在电解液中的浓度没有特别限制，只要能够实现本申请目的即可。例如，钠盐的浓度为1.0mol/L至2.0mol/L。
本申请的钠离子电池还包括壳体，本申请对壳体没有特别限制，本领域技术人员可以根据实际需要选择，只要能够实现本申请目的即可。例如，壳体可以包括铝塑膜。
本申请对钠离子电池的制备方法没有特别限制，可以选用本领域公知的制备方法，只要能够实现本申请目的即可。例如，钠离子电池的制备方法包括但不限于如下步骤：将正极极片、隔膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的裸电芯，将裸电芯放入包装袋内，将电解液注入包装袋并封口，得到钠离子电池。
本申请还提供了一种电池包，包括箱体和至少一个上述任一实施方案中的钠离子电池，钠离子电池收容于箱体中。具有该二电池的电池包的性能优异，有利于电池包的使用。通过将电池收容于箱体中可以增加对电池的固定和保护作用，提高电池包的使用寿命。可以理解的，电池包中可以具有一个或多个钠离子电池，当电池包含有多个钠离子电池时，多个钠离子电池可以通过并联和串联中的至少一种方式连接。
本申请还提供了一种用电设备，包括上述任一实施方案中的钠离子电池或电池包，有利于提升用电设备的产品竞争力和使用性能。在一种可选的实施方案中，用电设备包括用电设备本体，钠离子电池或电池包用于为用电设备本体供电。在一种可选的实施方案中，用电设备本体包括设备正极及设备负极，钠离子电池或电池包的正极极片用于电连接用电设备本体的设备正极，钠离子电池或电池包的负极极片用于电连接用电设备本体的设备负极，以对用电设备供电。
本申请的用电设备可以包括但不限于：集装箱、户用储能系统、电瓶车、电动汽车、轮船、航天器、电动玩具和电动工具等等，其中，航天器例如是飞机、火箭、航天飞机和宇宙飞船等等，电动玩具例如包括固定式或移动式的电动玩具，具体例如，电动汽车玩具、电动轮船玩具和电动飞机玩具等等，电动工具例如包括金属切削电动工具、研磨电动工具、装配电动工具和铁道用电动工具，具体例如，电钻、电动砂轮机、电动扳手、电动螺丝刀、电锤、冲击电钻、混凝土振动器和电刨。
请参见图1，图1为本申请一种实施方案的户用储能系统的结构示意图，且本申请图1实施方案以用户侧储能中的家用储能场景为例进行说明，本申请储能装置并不限定于家用储能场景。
本申请提供一种户用储能系统，该户用储能系统包括电能转换装置2(光伏板)、第一用户负载3(路灯)、第二用户负载4(例如空调等家用电器)等以及储能装置1，储能装置1为小型储能箱，可通过壁挂方式安装于室外墙壁。具体的，光伏板可以在电价低谷时期将太阳能转换为电能，储能装置1用于储存该电能并在电价高峰时供给路灯和家用电器进行使用，或者在电网断电/停电时进行供电。
请参见图2，图2为本申请一种实施方案的储能系统400的结构示意图，且本申请图2实施方案以发/配电侧共享储能场景为例进行说明，本申请储能装置1并不限定于其发/配电侧储能场景。
本申请提供了一种储能系统400，储能系统400包括：高压电缆410、第一电能转换装置420、第二电能转换装置430及本申请提供的储能装置1，发电情况下，第一电能转换装置420及第二电能转换装置430用于将其它形式的能源转换为电能，与高压电缆410连接并供给配网用电侧使用，当用电负荷较低，第一电能转换装置420、第二电能转换装置430发电过剩时，将多发的电量储存至储能装置1，减少弃风、弃光率，改善新能源发电消纳问题；在用电负荷高位时，电网下达指令，将储能装置1储存的电量协同高压电缆410采用并网模式传输电能供给用电侧使用，为电网运行提供调峰、调频、备用等多种服务，充分发挥电网调峰的作用，促进电网削峰填谷，缓解电网供电压力。
可选地，第一电能转换装置420及第二电能转换装置430可将太阳能、光能、风能、热能、潮汐能、生物质能及机械能等中的至少一种转换为电能。
储能装置1的数量可以为多个，多个储能装置1相互串联或并联，多个储能装置1采用隔离板(图未示)进行支撑及电连接。本实施方案中，“多个”是指两个及两个以上。储能装置1外部还可以设有储能箱，用于收容储能装置1。
可选地，储能装置1可包括但不限于单体电池、电池模组、电池包、电池系统等。本申请实施方案提供的储能装置1的实际应用形态可以为但不限于为所列举产品，还可以是其他应用形态，本申请实施方案不对储能装置1的应用形态做严格限制。本申请实施方案仅以储能装置1为多芯电池为例进行说明。当该储能装置1为单体电池时，储能装置1可以为圆柱电池、方形电池等中的至少一种。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。
实施例1
该实施例包括如下步骤：
补钠材料的制备：
将30g市售补钠剂Na2C4O4粉末加入到装有900mL去离子水的烧杯中，搅拌30min，使补钠剂完全溶解，得到补钠剂溶液；向补钠剂溶液中加入2500mL无水乙醇，搅拌60min，生成Na2C4O4沉淀；对沉淀采用无水乙醇进行抽滤，然后洗涤，得到底部沉淀，在110℃条件下真空干燥24h，得到再结晶Na2C4O4，也即经粒径调控处理后的Na2C4O4，D50为2.83μm；
称取10g制得的再结晶Na2C4O4，溶解于75mL无水乙醇中，经超声分散30min后得到分散液；将1.6mL钛酸四丁酯加入到所得分散液中，超声分散30min后，于60℃条件下干燥以去除乙醇，得到混合物；将所得混合物在氮气气氛下于360℃条件下煅烧4h，经破碎机破碎并过筛后，得到D50为1.12μm的补钠材料。其中，补钠材料中Na2C4O4的质量百分含量为90％，余量为二氧化钛。
补钠剂极片的制备：
将制得的补钠材料、导电剂科琴黑(Ketjen Black)、粘结剂PVDF按照质量比60∶30∶10混合，加入溶剂N-甲基吡咯烷酮(NMP)，并搅拌均匀，得到固含量为60％的补钠剂浆料，然后将补钠剂浆料均匀涂覆于10μm厚度的铝箔上，单面涂覆厚度为20μm，然后在110℃条件下真空干燥12h，得到补钠剂极片。将所得补钠剂极片裁剪为直径14μm的圆片待用。
NFPP正极极片的制备：
将正极活性材料Na4Fe3(PO4)2(P2O7)(即NFPP)、制得的补钠材料、导电剂科琴黑、粘结剂PVDF按照质量比70∶10∶10∶10混合，然后加入NMP，并搅拌均匀，得到固含量为60％的正极浆料，然后将正极浆料均匀涂覆于10μm厚度的铝箔上，单面涂覆厚度为20μm，然后在110℃条件下真空干燥12h，得到NFPP正极极片。将所得NFPP正极极片裁剪为直径14μm的圆片待用。
电解液的制备：
在水分含量≤1ppm的氩气气氛手套箱中，将碳酸亚乙酯(EC)、碳酸二乙酯(DEC)按照体积比1∶1进行混合，然后加入钠盐NaClO4并溶解到上述溶剂中，混合均匀后得到电解液。其中，NaClO4在电解液中的摩尔浓度为1mol/L。
隔膜的制备：
选用厚度为260μm的玻璃纤维膜作为隔膜。
扣式电池的组装：
第一扣式电池的组装：
使用直径为14μm的圆形钠片作为对电极，将上述制备得到的圆形补钠剂极片、隔膜和圆形钠片按顺序叠好，使隔膜处于圆形补钠剂极片和圆形钠片中间起到隔离的作用，然后注入制备的电解液，组装成第一扣式电池。
第二扣式电池的组装：
使用直径为14μm的圆形钠片作为对电极，将上述制备得到的NFPP正极极片、隔膜和圆形钠片按顺序叠好，使隔膜处于NFPP正极极片和圆形钠片中间起到隔离的作用，然后注入制备的电解液，组装成第二扣式电池。
实施例2～实施例4
除了在补钠材料的制备中，按照表1调整补钠剂的种类以外，其余与实施例1相同。
实施例5～实施例7
除了在补钠材料的制备中，调整催化剂前驱体的种类以按照表1调整金属氧化物催化剂的种类以外，其余与实施例1相同。其中，实施例5的催化剂前驱体为2-乙基己酸钴，实施例6的催化剂前驱体为二乙基己酸锰，实施例7的催化剂前驱体为二乙基己酸亚锡。
实施例8～实施例10
除了在补钠材料的制备中，按照表1调整补钠剂和金属氧化物催化剂在补钠材料中的含量以外，其余与实施例1相同。
实施例11
除了在补钠材料的制备中，调整煅烧温度为400℃、煅烧时间为3h以外，其余与实施例1相同。
实施例12
除了在补钠材料的制备中，调整煅烧温度为500℃、煅烧时间为2h以外，其余与实施例1相同。
对比例1
除了将实施例1制得的再结晶Na2C4O4直接作为补钠材料使用以外，其余与实施例1相同。
对比例2
除了将市售补钠剂Na2C4O4直接作为补钠材料使用以外，其余与实施例1相同。
对比例3
不进行补钠材料的制备，也即，不制备第一扣式电池，并且NFPP正极极片中不含补钠材料使制得的第二扣式电池中也不含补钠材料以外，其余与实施例1相同。
NFPP正极极片的制备：
将正极活性材料NFPP、科琴黑、PVDF按照质量比80∶10∶10混合，然后加入NMP，并搅拌均匀，得到固含量为60％的正极浆料，然后将正极浆料均匀涂覆于10μm厚度的铝箔上，单面涂覆厚度为20μm，然后在110℃条件下真空干燥12h，得到NFPP正极极片。将所得NFPP正极极片裁剪为直径14μm的圆片待用。
对比例4
除了补钠材料的制备与实施例1不同以外，其余与实施例1相同。
补钠材料的制备：
称取10g市售补钠剂Na2C4O4粉末，与市售TiO2催化剂(Alfa-039953)按照质量比90∶10混合，搅拌均匀后得到混合物，将所得混合物作为补钠材料。
测试方法和设备：
金属元素含量测试：
利用SEM仪器(型号SU8010)的聚焦电子束激发补钠材料表面的选定区域产生二次电子、背散射电子和特征X射线等二次信息，收集检测这些二次信息并进行成分定量分析。具体地，选取补钠材料表面的任意500nm×500nm矩形区域，作为第一区域，对第一区域进行第一次EDS测试，得到属于金属氧化物催化剂的金属元素的含量，记为C0；然后通过SEM装置在10kV加速电压下对该第一区域进行热处理5min，使第一区域的补钠材料熔融，并对熔融后的第一区域进行第二次EDS测试，得到属于金属氧化物催化剂的金属元素的含量，记为C1。
氧化分解电位测试：
采用蓝电(LAND)测试系统对第一扣式电池进行首圈充放电测试，得到dQ/dV曲线，dQ/dV曲线氧化峰值对应补钠材料的氧化分解反应，dQ/dV曲线氧化峰值所对应的电位即为补钠材料的氧化分解电位。
材料粒径测试：
利用激光粒度分析仪测试补钠材料的平均粒径D50。
首圈充电容量、首圈放电容量测试：
测试温度为25℃，将扣式电池以0.1倍率(C)恒流充电至4V，此为充电阶段；静置10min，然后以0.1C恒流放电至2V，静置10min，此为放电阶段。记录第一次充电阶段的充电容量，作为首圈充电容量，单位mAh/g；记录第一次放电阶段的放电容量，作为首圈放电容量，单位mAh/g。
循环性能测试：
测试温度为25℃，将扣式电池以0.1C恒流充电到4V，静置10min后以0.1C放电到2V。以此步得到的容量为初始放电容量Ci，进行0.1C充电/0.1C放电的循环测试20圈(cycles)，记录第20圈循环的放电容量。循环容量保持率＝(第20圈循环的放电容量/初始放电容量Ci)×100％。
表1各实施例和对比例的补钠材料的数据


表1中，“/”表示不存在相关制备参数。
表2各实施例和对比例的第一扣式电池的性能数据

表2中，“/”表示不存在相关测试参数。
结合表1和表2，从实施例1与对比例1和对比例2可以看出，当仅是简单地对市售补钠剂进行再结晶处理(例如对比例1)或者直接使用市售补钠剂(例如对比例2)作为补钠材料时，由于对比例1和对比例2的补钠材料中不含有金属氧化物催化剂，因此经两次EDS测试后，不具有属于金属氧化物催化剂的金属元素的含量，同时也表明对比例1和对比例2的补钠材料不具有补钠剂包覆金属氧化物催化剂的复合结构。并且，对比例1和对比例2补钠材料的氧化分解电位高，第一扣式电池的首圈充电容量偏低，因此难以提高补钠材料的首圈补钠效果；从实施例1与对比例4可以看出，当仅是简单地将市售补钠剂与市售TiO2催化剂进行物理混合后作为补钠材料时，经两次EDS测试后，C1＜C0，表明对比例4的补钠材料同样不具有补钠剂包覆金属氧化物催化剂的复合结构。并且，对比例4补钠材料的氧化分解电位高，第一扣式电池的首圈充电容量低，因此难以提高补钠材料的首圈补钠效果。而本申请的补钠材料经两次EDS测试后，C1＞C0，表明补钠材料具有补钠剂包覆金属氧化物催化剂的复合结构，使得补钠材料具有低氧化分解电位，第一扣式电池的首圈充电容量得到明显提高，从而提高补钠材料的首圈补钠效果。
图3为实施例1制得的补钠材料的SEM图，从图3中可以看出，补钠剂Na2C4O4表面无明显的TiO2颗粒存在，这也印证了本申请的补钠材料具有补钠剂包覆金属氧化物催化剂的复合结构。
图4为对比例4制得的补钠材料的SEM图，从图4中可以看出，TiO2颗粒只是分散在补钠剂Na2C4O4的表面，并未形成补钠剂包覆金属氧化物催化剂的复合结构。
补钠剂、金属氧化物催化剂的种类、含量、补钠材料的粒径也会对钠离子电池的性能产生影响。从实施例2～实施例10可以看出，在C1＞C0的前提下，通过调控补钠剂、金属氧化物催化剂的种类和含量以及补钠材料的粒径在本申请范围内，有利于得到具有高首圈充电容量的钠离子电池。
煅烧时间和煅烧温度也会对钠离子电池的性能产生影响。从实施例11～实施例12可以看出，在C1＞C0的前提下，通过调控煅烧时间和煅烧温度在本申请范围内，有利于得到具有高首圈充电容量的钠离子电池。
表3各实施例和对比例的第二扣式电池的性能数据

结合表1和表3，从实施例1与对比例1～对比例4可以看出，当仅是简单地对市售补钠剂进行再结晶处理(例如对比例1)，或者直接使用市售补钠剂(例如对比例2)作为补钠材料，或者正极极片中不含补钠材料(例如对比例3)，或者将市售补钠剂与市售TiO2催化剂进行物理混合后作为补钠材料(例如对比例4)时，由于对比例1、对比例2和对比例4的补钠材料不具有补钠剂包覆金属氧化物催化剂的复合结构，对比例3的正极极片中不含补钠材料，第二扣式电池的首圈充电容量和首圈放电容量均较低，导致首圈库伦效率低，因此不利于钠离子电池能量密度和循环性能的提升；而本申请的第二扣式电池的首圈充电容量、首圈放电容量和20圈循环后容量保持率均显著提高，从而有利于钠离子电池能量密度和循环性能的提升。
补钠剂、金属氧化物催化剂的种类、含量、补钠材料的粒径也会对钠离子电池的性能产生影响。从实施例2～实施例10可以看出，在C1＞C0的前提下，通过调控补钠剂、金属氧化物催化剂的种类和含量以及补钠材料的粒径在本申请范围内，有利于得到具有高首圈充电容量、高首圈放电容量和优异循环性能的NFPP钠离子电池。
煅烧时间和煅烧温度也会对钠离子电池的性能产生影响。从实施例11～实施例12可以看出，在C1＞C0的前提下，通过调控煅烧时间和煅烧温度在本申请范围内，有利于得到具有高首圈充电容量、高首圈放电容量和优异循环性能的NFPP钠离子电池。
图5为实施例1的第一扣式电池的首圈充电过程的dQ/dV微分容量曲线图；图6为对比例1的第一扣式电池的首圈充电过程的dQ/dV微分容量曲线图。从图5可以看出，实施例1的氧化峰电位为4.12V；从图6可以看出，对比例1的氧化峰电位为4.25V，表明本申请的补钠材料具有更低的氧化分解电位，有利于提高首圈补钠效果。
图7为实施例1的第二扣式电池的首圈充放电曲线；图8为对比例3的第二扣式电池的首圈充放电曲线。从图7可以看出，实施例1的第二扣式电池首圈充电容量提升至138.4mAh/g，并且在4.12V左右显示出一个氧化平台，这部分平台提供的容量对应于补钠材料的氧化分解过程；从图8可以看出，对比例3的首圈充电容量为115.7mAh/g，其首圈充电平台在约2.8V、2.95V和3.28V处显示出氧化平台，分别对应于Na3位点、Na1位点和Na4位点的Na脱出过程。进一步地，实施例1的首圈放电比容量105.1mAh/g，对比例3的首圈放电比容量为101.5mAh/g，且实施例1的20圈循环后容量保持率相比于对比例1也得到提升，这表明本申请补钠材料的加入对NFPP正极极片后续循环过程中的结构不会产生影响，甚至起到积极作用。由上可知，本申请的补钠材料能够有效弥补NFPP正极极片的首圈钠损失，显示出与NFPP正极极片的良好兼容性，有利于钠离子电池能量密度和循环性能的提升。
以上对本申请实施例公开的一种补钠材料及其制备方法、正极极片、钠离子电池进行了详细的介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请实施例的技术方案及核心发明点：同时，对于本领域的一般技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上，本说明书内容不应理解为对本申请的限制。

Claims (16)

  1. 一种补钠材料，其中，包括补钠剂NaxCyOzHw和金属氧化物催化剂，1≤x≤3，1≤y≤6，1≤z≤7，0≤w≤5；
    对所述补钠材料表面的任意第一区域进行第一次EDS测试，测得属于所述金属氧化物催化剂的金属元素的含量为C0，对熔融后的所述第一区域进行第二次EDS测试，测得属于所述金属氧化物催化剂的金属元素的含量为C1，C1＞C0。
  2. 根据权利要求1所述的补钠材料，其中，所述补钠材料具有所述补钠剂包覆所述金属氧化物催化剂的复合结构。
  3. 根据权利要求1或者2所述的补钠材料，其中，所述补钠材料的氧化分解电位为Epa，满足4.10V≤Epa≤4.20V。
  4. 根据权利要求1～3中任一项所述的补钠材料，其中，所述补钠材料的中值粒径D50为0.8μm～2μm。
  5. 根据权利要求1～4中任一项所述的补钠材料，其中，基于所述补钠材料的总质量为100％，所述补钠剂的质量百分含量为70％～95％，所述金属氧化物催化剂的质量百分含量为5％～30％。
  6. 根据权利要求1～5中任一项所述的补钠材料，其中，所述补钠剂选自CH3COONa、C6H5Na3O7、Na2C4O4、Na2CO3、Na2C2O4和Na2C6O6中的至少一种。
  7. 根据权利要求1～6任一项所述的补钠材料，其中，所述金属氧化物催化剂选自二氧化钛、二氧化钌、二氧化锰、二氧化钼、四氧化三钴、四氧化三铁和二氧化锡中的至少一种。
  8. 一种如权利要求1～7任一项所述的补钠材料的制备方法，其中，包括以下步骤：
    将经粒径调控处理后的补钠剂与醇基溶剂混合，得到分散液，其中，经粒径调控处理后的所述补钠剂的中值粒径D50为1μm～3μm；
    将催化剂前驱体加入到所述分散液中进行混合，干燥后得到混合物；
    将所述混合物在气体气氛下进行煅烧，煅烧温度为300℃～500℃，煅烧时间为1h～6h，得到所述补钠材料。
  9. 根据权利要求8所述的制备方法，其中，所述方法还包括：
    通过再结晶处理、球磨处理、破碎处理或者喷雾干燥处理调控所述补钠剂的粒径分布，得到所述粒径调控处理后的补钠剂。
  10. 根据权利要求8或9所述的制备方法，其中，所述催化剂前驱体选自钛酸四丁酯、二乙基己酸锰、二乙基己酸铁、二乙基己酸铜、2-乙基己酸钴、二乙基己酸镍和二乙基己酸亚锡中的至少一种。
  11. 根据权利要求8～10中任一项所述的制备方法，其中，所述醇基溶剂自甲醇、乙醇和乙二醇中的至少一种。
  12. 根据权利要求8～11中任一项所述的制备方法，其中，所述气体气氛包括氩气、氮气和空气中的任一种。
  13. 一种正极极片，其中，包括集流体和设置于所述集流体至少一个表面的正极活性材料层，所述正极活性材料层包括如权利要求1～7任一项所述的补钠材料，或者包括如权利要求8～12任一项所述的制备方法制得的补钠材料。
  14. 一种钠离子电池，其中，包括权利要求13所述的正极极片。
  15. 一种电池包，其中，包括箱体和至少一个权利要求14所述的钠离子电池，所述钠离子电池收容于所述箱体中。
  16. 一种用电设备，其中，包括权利要求14所述的钠离子电池，或者，包括权利要求15所述的电池包。
PCT/CN2024/138741 2024-03-18 2024-12-12 补钠材料及其制备方法、正极极片、钠离子电池、电池包和用电设备 Pending WO2025194875A1 (zh)

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CN121641953A (zh) * 2024-09-02 2026-03-10 宁德时代新能源科技股份有限公司 二次电池、正极不可逆添加剂及其制备方法、用电设备
CN121376952B (zh) * 2025-12-22 2026-03-20 四川华芯智宇新能源科技有限公司 一种聚阴离子钠离子电池正极复合材料
CN121394310B (zh) * 2025-12-23 2026-03-24 浙江华宇钠电新能源科技有限公司 一种石墨烯基钠电正极的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117133862A (zh) * 2023-10-27 2023-11-28 宁德时代新能源科技股份有限公司 正极极片及其制备方法以及电池、用电设备
CN117154003A (zh) * 2023-10-31 2023-12-01 宁德时代新能源科技股份有限公司 一种正极极片、制备方法、钠二次电池和用电装置
CN118198364A (zh) * 2024-03-18 2024-06-14 厦门海辰储能科技股份有限公司 补钠材料及其制备方法、正极极片、钠离子电池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104437484B (zh) * 2014-12-01 2016-08-24 嘉兴学院 一种合成金属/金属氧化物负载型纳米催化剂的方法
CN111834622B (zh) * 2020-07-22 2022-10-25 华中科技大学 一种具有补锂/钠功能的多层正极片、电池以及制备方法
CN113113681B (zh) * 2021-04-12 2022-05-10 中国科学院化学研究所 一种复合补钠添加剂及在钠离子电池中的应用
CN115295790A (zh) * 2022-09-05 2022-11-04 无锡钠科能源科技有限公司 一种钠离子电池正极材料的包覆方法
CN115385397A (zh) * 2022-09-16 2022-11-25 惠州亿纬锂能股份有限公司 一种补钠正极材料及其制备方法和应用
CN116779867A (zh) * 2023-08-03 2023-09-19 上海大学 一种正极补钠添加剂、包含其的正极极片及其在钠离子电池中的应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117133862A (zh) * 2023-10-27 2023-11-28 宁德时代新能源科技股份有限公司 正极极片及其制备方法以及电池、用电设备
CN117154003A (zh) * 2023-10-31 2023-12-01 宁德时代新能源科技股份有限公司 一种正极极片、制备方法、钠二次电池和用电装置
CN118198364A (zh) * 2024-03-18 2024-06-14 厦门海辰储能科技股份有限公司 补钠材料及其制备方法、正极极片、钠离子电池

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