CN113896240A - Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery - Google Patents

Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery Download PDF

Info

Publication number
CN113896240A
CN113896240A CN202111165310.5A CN202111165310A CN113896240A CN 113896240 A CN113896240 A CN 113896240A CN 202111165310 A CN202111165310 A CN 202111165310A CN 113896240 A CN113896240 A CN 113896240A
Authority
CN
China
Prior art keywords
sodium
compound
positive electrode
ion battery
sulfide
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
CN202111165310.5A
Other languages
Chinese (zh)
Inventor
闫勇
黄学杰
田孟羽
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.)
Songshanhu Dongguan Material Technology Development Co ltd
Songshan Lake Materials Laboratory
Original Assignee
Songshan Lake Materials Laboratory
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Songshan Lake Materials Laboratory filed Critical Songshan Lake Materials Laboratory
Priority to CN202111165310.5A priority Critical patent/CN113896240A/en
Publication of CN113896240A publication Critical patent/CN113896240A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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

Abstract

The application relates to the technical field of energy storage, in particular to a compound for pre-sodium treatment and a preparation method thereof, a positive electrode pre-sodium treatment material and a preparation method thereof, and a sodium ion battery. The chemical formula of the compound for pre-sodium treatment is NaxMyOzWherein x is more than or equal to 3 and less than or equal to 7, y is more than or equal to 1 and less than or equal to 2, z is more than or equal to 4 and less than or equal to 7, and M is one or more of Nb, Ta or V. The compound is applied to a sodium ion battery, and in the charging process of the battery, the compound is irreversibly decomposed to release active sodium ions, thereby supplementing active sodium loss caused by the growth of a negative electrode SEIThe effects of improving the energy density and prolonging the cycle life of the sodium ion battery can be achieved. According to the positive electrode pre-sodium material, the compound is arranged, so that the decomposition potential is low, the charging specific capacity is high, the discharging process is irreversible, and a good sodium ion battery in-situ pre-sodium effect can be realized. The positive electrode pre-sodium material provided by the application has good air stability, can be compatible with the existing sodium ion battery production process, and has a commercial application prospect.

Description

Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery
Technical Field
The application relates to the technical field of energy storage, in particular to a compound for pre-sodium treatment and a preparation method thereof, a positive electrode pre-sodium treatment material and a preparation method thereof, and a sodium ion battery.
Background
In the first cycle process of the sodium ion energy storage device, a Solid Electrolyte Interface (SEI) is formed at a negative electrode interface, so that irreversible capacity loss is generated, and the energy density of the sodium ion energy storage device is reduced due to the reduction of the content of active sodium. Hard carbon is selected as a negative electrode material in the sodium ion battery, the hard carbonization degree is low, the porosity is high, the first coulombic efficiency is low, the first-cycle capacity loss of the sodium ion battery is high, and the energy density of the sodium ion battery needs to be improved through an in-situ pre-sodium treatment technology.
The existing sodium ion battery sodium supplementing technology mainly has two modes of anode pre-sodium modification and cathode pre-sodium modification, wherein the cathode pre-sodium modification needs to use metal sodium, and the metal sodium has higher activity compared with metal lithium, poorer air stability and more danger, so that the cathode pre-sodium modification process is complex, the operating environment requirement is high and the potential safety hazard is large.
The prior positive electrode pre-sodium treatment technology is characterized in that a sodium compound, such as sodium oxide, is added to the positive electrode of a sodium-ion battery: sodium oxide, sodium peroxide, sodium superoxide; organic compounds of sodium: trisodium cyanurate, sodium ascorbate, sodium urate; in sodium compounds selected in the prior art, sodium oxide has high activity, poor air stability and high safety risk, and is difficult to realize large-scale application under the existing sodium ion battery technology. The sodium organic compound has lower sodium removal specific capacity, is used as a pre-sodium material to improve the energy density of the sodium ion battery less, and can generate CO in the sodium removal decomposition process2、O2And the sodium ion battery causes negative effects.
Disclosure of Invention
The embodiment of the application aims to provide a novel compound for pre-sodium treatment and a preparation method thereof, a positive electrode pre-sodium treatment material and a preparation method thereof, and a sodium ion battery.
In a first aspect, the application provides a compound for pre-sodium treatment, the compound for pre-sodium treatment has a chemical formula of NaxMyOz, wherein x is more than or equal to 3 and less than or equal to 7, y is more than or equal to 1 and less than or equal to 2, z is more than or equal to 4 and less than or equal to 7, and M is one or more of Nb, Ta or V.
The compound is applied to a sodium ion battery, and in the charging process of the battery, the compound is irreversibly decomposed to release active sodium ions, so that the loss of active sodium caused by the growth of a negative electrode SEI is supplemented, and the effects of improving the energy density and prolonging the cycle life of the sodium ion battery can be achieved.
In other embodiments of the present application, the above-mentioned compounds for pre-sodium treatment include: na (Na)5NbO5、Na3NbO4、Na4Nb2O7、Na5VO5、Na3VO4、Na5TaO5Or Na3TaO4。
In other embodiments of the present application, the particle size of the above-described compound for pre-sodium treatment is in the range of 10nm to 100 μm.
In a second aspect, the present application provides a positive electrode pre-sodium treatment material comprising the compound for pre-sodium treatment of any one of the foregoing.
The application provides a positive pole is sodium material in advance through setting up aforementioned compound for decomposition potential is lower, and the specific capacity that charges is high, and the discharge process is irreversible, can realize better sodium ion battery normal position sodium effect in advance. The positive electrode pre-sodium material provided by the application has good air stability, can be compatible with the existing sodium ion battery production process, and has a commercial application prospect.
In other embodiments of the present application, the positive electrode pre-sodium treatment material further includes a reducing agent; optionally, the ratio of the reducing agent to the compound for pre-sodium treatment is (1: 100) - (1:1) in terms of mass ratio;
optionally, the reducing agent comprises: at least one of boride, sulfide, phosphide or reducing simple substance;
optionally, the boride comprises: at least one of cobalt boride, molybdenum boride, calcium boride, aluminum boride, magnesium boride, titanium boride, zirconium boride, tungsten boride, or lanthanum boride;
alternatively, the sulfide compound comprises: at least one of sodium sulfide, iron sulfide, cobalt sulfide, molybdenum sulfide, tungsten sulfide, titanium sulfide, magnesium sulfide, calcium sulfide, lanthanum sulfide, or tantalum sulfide;
optionally, the phosphide includes: at least one of iron phosphide, boron phosphide, nickel phosphide, sodium phosphide, or zinc phosphide;
alternatively, the reducing element comprises: at least one of elemental sulfur, elemental phosphorus, elemental boron, elemental silicon, elemental aluminum, elemental germanium, elemental arsenic, elemental iodine, elemental vanadium, elemental manganese, elemental iron, elemental cobalt, elemental nickel, or elemental tin.
In other embodiments of the present application, the positive electrode pre-sodium treatment material further includes a coating layer, and the coating layer is coated on the surface of the compound for pre-sodium treatment; or the coating layer is coated on the surface of the mixture of the compound for pre-sodium treatment and the reducing agent;
wherein the coating layer comprises any one of a carbon coating layer or a conductive polymer coating layer.
In a third aspect, the present application provides a method for preparing a compound for pre-sodium treatment, comprising:
mixing an M source and a sodium source, and sintering at 600-1100 ℃;
wherein when the M source is mixed with the sodium source, the ratio of the metal element M: molar ratio of Na ═ y: [ x (1.2-0.8) ] mixing; the M source comprises at least one of an oxide of the metal M, a carbonate of the metal M, a nitrate of the metal M, a sulfate of the metal M, a chloride of the metal M, a hydroxide of the metal M or an organic compound of the metal M;
the sodium source includes at least one of sodium carbonate, sodium hydroxide, sodium nitrate, sodium chloride, or sodium oxide.
In a fourth aspect, the present application provides a method for preparing a pre-sodiumized positive electrode material, comprising:
mixing any one of the compounds for pre-sodium treatment defined by the formula or defined by the preparation method with a reducing agent; or
Any of the aforementioned compounds defined by chemical formula or defined by manufacturing method for pre-sodium treatment is mixed with an electrolyte, a reducing additive.
In other embodiments of the present application, the method comprises: coating the compound for pre-sodium treatment to form a coating layer on the surface of the compound, and then mixing the compound with a reducing agent; or mixed with electrolyte and reducing additive.
In a fifth aspect, the present application provides a sodium ion battery comprising the positive electrode pre-sodiumized material of any one of the preceding; or the positive electrode pre-sodium material prepared by the preparation method of the positive electrode pre-sodium material.
The application provides a sodium ion battery, in the battery charging process, the compound irreversibly decomposes and releases active sodium ion, has replenished the active sodium loss that negative pole SEI grows to lead to, has promoted sodium ion battery energy density and life cycle's effect.
In another embodiment of the present application, a reducing additive is added to the electrolyte of the sodium ion battery; optionally, the addition amount of the reducing additive in the electrolyte is 0.01-10% by mass;
optionally, the reducing additive comprises at least one of vinylene carbonate, vinylene trithiocarbonate, vinyl sulfite, propane sultone, butane sultone, vinyl sulfate, vinyl sulfite, dimethyl sulfide, dimethyl disulfide, methyl ethyl sulfide, tetrahydrothiophene, or sodium bisoxalate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a scanning electron microscope image of the pre-sodium material of the positive electrode in example 1 of the present application;
fig. 2 is a charge/discharge curve of the positive electrode pre-sodium material in example 1 of the present application.
Detailed Description
Hereinafter, embodiments of the present application will be described in detail so that those skilled in the art to which the present application pertains can easily carry out the present application. The embodiments of the present application are provided to more fully explain the present application to those of ordinary skill in the art. Therefore, the embodiments of the present application may be modified into various different forms, and the scope of the present application is not limited to the embodiments described below.
Throughout the specification of the present application, when a portion is described as "including" a certain structural element, it is meant that other structural elements may be included, without excluding other structural elements, unless otherwise noted.
Throughout the specification of the present application, when it is described that a certain step is "on" or "before" other steps, this includes not only a case where a certain step has a direct chronological relationship with other steps but also the same right as a case where an indirect chronological relationship in which the order of two steps such as a mixing step after each step is changeable.
The terms "about," "substantially," and the like, as used throughout this specification to refer to a degree which is indicative of inherent manufacturing and material tolerances, are used in the meaning of a value or close to the value, to prevent the disclosure of an exact or absolute value being unduly employed by an unscrupulous infringer to assist in the invention.
The embodiment of the application provides a compound for pre-sodium treatment, wherein the chemical formula of the compound for pre-sodium treatment is NaxMyOzWherein x is more than or equal to 3 and less than or equal to 7, y is more than or equal to 1 and less than or equal to 2, z is more than or equal to 4 and less than or equal to 7, and M is one or more of Nb, Ta or V.
Illustratively, the chemical formula of the above-mentioned compound for pre-sodium treatment is NaxMyOzWherein x is selected from 3, 4, 5, 6 and 7; y is selected from 1, 1.2, 1.5, 1.8 and 2; z is selected from 4, 5, 6, 7. Wherein x, y and z have values such that Na, M and O are converted toAnd (4) balancing the valence. For example, when y is 1.2, M may be Ta and/or V, x may be 2 or 6, and z may be 4 or 6, respectively.
Illustratively, the chemical formula of the above-mentioned compound for pre-sodium treatment is NaxMyOzWherein M is any one of Nb, Ta or V; or M is any two of Nb, Ta or V, for example: m is Nb and Ta; m is V and Nb; m is Ta and V; or M is three of Nb, Ta or V.
In some embodiments of the present application, the above-mentioned compound for pre-sodium treatment includes: na (Na)5NbO5、Na3NbO4、Na4Nb2O7、Na5VO5、Na3VO4、Na5TaO5Or Na3TaO4。
Further, the particle size of the above-mentioned compound for pre-sodium treatment is in the range of 10nm to 100 μm.
Further optionally, the particle size of the above compound for pre-sodium treatment is in the range of 11nm-99 μm. Further optionally, the particle size of the above compound for pre-sodium treatment is in the range of 15nm-90 μm.
Illustratively, the particle size of the above-mentioned compound for pre-sodium treatment is 20nm, 50nm, 100nm, 1 μm, 20 μm, 50 μm or 80 μm.
Some embodiments of the present application provide a positive electrode pre-sodium treatment material, including the compound for pre-sodium treatment provided in any one of the preceding embodiments.
Further, in some embodiments of the present application, the above-mentioned positive electrode pre-sodium treatment material further includes a reducing agent.
The reducing agent is added to reduce the decomposition potential of the compound for pre-sodium treatment, promote the compound to decompose and release active sodium ions, and supplement the active sodium loss caused by the growth of the SEI of the negative electrode, so that the effects of improving the energy density and prolonging the cycle life of the sodium ion battery are achieved.
Further, the ratio of the reducing agent to the compound for pre-sodium treatment is (1: 100) to (1:1) in terms of mass ratio.
Further optionally, the ratio of the reducing agent to the compound for pre-sodium treatment is (1: 90) - (1:1) in terms of mass ratio.
Further optionally, the ratio of the reducing agent to the compound for pre-sodium treatment is (1: 80) - (1:1) in terms of mass ratio.
Illustratively, the ratio of reducing agent to compound for pre-sodium modification is 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:5, or 1:2, by mass ratio.
Further, the reducing agent includes: at least one of boride, sulfide, phosphide or reducing simple substance.
In some embodiments of the present application, the boride comprises: cobalt boride, molybdenum boride, calcium boride, aluminum boride, magnesium boride, titanium boride, zirconium boride, tungsten boride, or lanthanum boride.
In some embodiments of the present application, the sulfide comprises: at least one of sodium sulfide, iron sulfide, cobalt sulfide, molybdenum sulfide, tungsten sulfide, titanium sulfide, magnesium sulfide, calcium sulfide, lanthanum sulfide, or tantalum sulfide.
In some embodiments of the present application, the phosphide comprises: at least one of iron phosphide, boron phosphide, nickel phosphide, sodium phosphide, or zinc phosphide.
In some embodiments of the present application, the reducing element comprises: at least one of elemental sulfur, elemental phosphorus, elemental boron, elemental silicon, elemental aluminum, elemental germanium, elemental arsenic, elemental iodine, elemental vanadium, elemental manganese, elemental iron, elemental cobalt, elemental nickel, or elemental tin.
In some embodiments of the present application, the above-described positive electrode pre-sodium treatment material further comprises a coating layer. The coating layer is coated on the surface of the compound for pre-sodium treatment; or the coating layer is coated on the surface of the mixture of the compound for pre-sodium treatment and the reducing agent.
Further, the coating layer includes a carbon coating layer or a conductive polymer coating layer.
Some embodiments of the present application provide a method for preparing a compound for pre-sodium treatment, comprising the steps of:
and step S1, mixing the M source with the sodium source.
Further, when the M source is mixed with the sodium source, the ratio of the metal element M: molar ratio of Na ═ y: [ x (1.2-0.8) ] mixing.
In some embodiments of the present application, the source of M and the source of sodium are mixed in terms of the metal element M: molar ratio of Na ═ y: [ x (1.2-0.8) ] to obtain a mixture.
Further optionally, mixing the M source and the sodium source according to the ratio of the metal element M: molar ratio of Na ═ y: [ x (1.15-0.85) ] to get mixture.
Illustratively, the M source and the sodium source are mixed in the following manner as the metal element M: molar ratio of Na ═ y: [ x 1.0 ]; m: molar ratio of Na ═ y: [ x 1.05 ]; m: molar ratio of Na ═ y: [ x 0.9 ]; uniformly mixing or grinding to obtain a mixture.
Further, the M source includes at least one of an oxide of the metal M, a carbonate of the metal M, a nitrate of the metal M, a sulfate of the metal M, a chloride of the metal M, a hydroxide of the metal M, and an organic compound of the metal M.
Illustratively, in some embodiments of the present application, the source of M is selected from the oxides or hydroxides of the metal M.
In some embodiments of the present application, the source of M is selected from a mixture of oxides and hydroxides of the metal M.
In some embodiments of the present application, the source of M is selected from any one of an oxide, a carbonate, a nitrate, a sulfate, a chloride, a hydroxide, and an organic compound of the metal M.
Further, the sodium source includes at least one of sodium carbonate, sodium hydroxide, sodium nitrate, sodium chloride, or sodium oxide.
Illustratively, in some embodiments of the present application, the sodium source is selected from any one of sodium carbonate, sodium hydroxide, and sodium oxide.
In some embodiments of the present application, the sodium source is selected from sodium carbonate and sodium hydroxide.
In some embodiments of the present application, the sodium source is selected from sodium hydroxide and sodium oxide.
And step S2, sintering.
Further, when the mixture obtained in step S1 is sintered, the sintering temperature is 600 to 1100 ℃.
Further optionally, the sintering temperature is 650-1000 ℃; illustratively, the sintering temperature is 700 ℃, 800 ℃, 900 ℃ or 950 ℃.
Some embodiments of the present disclosure provide a method of preparing a positive electrode pre-sodium material, including: the compound for pre-sodium treatment provided in any one of the preceding embodiments or the compound for pre-sodium treatment prepared by the method for preparing the compound for pre-sodium treatment provided in any one of the preceding embodiments is mixed with a reducing agent.
Further, in some embodiments of the present application, the method for preparing the positive electrode pre-sodium treatment material further comprises preparing a coating layer.
In some embodiments of the present application, the coating layer is a carbon coating layer, and further optionally, the step of preparing the carbon coating layer includes:
and adding a carbon source in the mixing process of the metal M source and the sodium source to obtain a mixture, and sintering the mixture in an inert or reducing atmosphere to obtain the positive electrode pre-sodium material containing the carbon coating layer.
In some embodiments of the present application, the step of preparing the carbon coating layer comprises:
and sintering the sintered positive electrode pre-sodium material in gas containing carbon molecules such as acetylene, ethylene, toluene and the like to prepare the positive electrode pre-sodium material containing the carbon coating layer.
In some embodiments of the present application, the coating layer is a conductive polymer coating layer, and further optionally, the step of preparing the conductive polymer coating layer includes:
and uniformly mixing or grinding the sintered positive electrode pre-sodium material and the conductive polymer to prepare the positive electrode pre-sodium material coated with the conductive polymer.
In some embodiments of the present application, the step of preparing the conductive polymer coating layer comprises:
and uniformly mixing or grinding the sintered positive electrode pre-sodium material with a conductive polymer solution, and drying to obtain the positive electrode pre-sodium material coated with the conductive polymer.
In some embodiments of the present application, the step of preparing the conductive polymer coating layer comprises:
and polymerizing the surface of the sintered positive electrode pre-sodium material by using a conductive polymer monomer or a small molecular compound to obtain the positive electrode pre-sodium material coated with the conductive polymer.
Some embodiments of the present application provide a sodium ion battery comprising the positive electrode pre-sodium material provided in any of the preceding embodiments; or the positive electrode pre-sodium material prepared by the preparation method of the positive electrode pre-sodium material provided by any one of the foregoing embodiments.
In some embodiments of the present application, a reducing additive is added to the electrolyte of the sodium ion battery.
The reductive additive is added into the electrolyte, so that the decomposition potential of the compound for pre-sodium treatment can be reduced, the compound is promoted to decompose and release active sodium ions, and the loss of active sodium caused by the growth of a negative electrode SEI is supplemented, so that the effects of improving the energy density and prolonging the cycle life of the sodium ion battery are achieved.
In some embodiments of the present application, the reducing additive is added to the electrolyte in an amount of 0.01 to 10% by mass.
Further optionally, the addition amount of the reducing additive in the electrolyte is 0.02-9.8% by mass. Further optionally, the addition amount of the reducing additive in the electrolyte is 0.2-5% by mass. Illustratively, the amount of the reducing additive added to the electrolyte solution is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8% by mass.
In some embodiments of the present application, the reducing additive includes at least one of vinylene carbonate, vinylene trithiocarbonate, vinyl sulfite, propane sultone, butane sultone, vinyl sulfate, vinyl sulfite, dimethyl sulfide, dimethyl disulfide, methyl ethyl sulfide, tetrahydrothiophene, or sodium bisoxalate.
Further, in some embodiments of the present application, the positive pre-sodiumizing material accounts for 0.1% to 20% of the active material of the positive plate of the sodium-ion battery by mass ratio. Further optionally, the positive pre-sodium material accounts for 1% -19% of the active material of the positive pole piece of the sodium-ion battery in terms of mass ratio. Further optionally, the positive pre-sodium material accounts for 1-5% of the active material of the positive pole piece of the sodium-ion battery in terms of mass ratio. Illustratively, the positive electrode pre-sodium material accounts for 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15% or 18% of the active material of the positive electrode plate of the sodium-ion battery in terms of mass ratio.
In some embodiments of the present application, in the sodium ion battery, the foregoing application manner in the sodium ion battery positive electrode pre-sodium treatment material includes, but is not limited to, the following:
(1) mixing the sodium-ion battery positive electrode material powder with the sodium-ion battery positive electrode pre-sodium material powder, and then preparing a positive electrode piece added with the pre-sodium positive electrode material;
(2) adding a sodium ion battery anode pre-sodium material in the pulping process of the sodium ion battery anode material, and then coating to obtain an anode piece added with the pre-sodium anode material;
(3) coating a sodium ion battery positive electrode pre-sodium material on the surface of a sodium ion battery positive electrode plate to obtain a positive electrode plate added with the pre-sodium material;
(4) coating a sodium ion battery positive electrode pre-sodium material on one side of a sodium ion battery diaphragm, and assembling the side coated with the positive electrode pre-sodium material close to a positive electrode pole piece into a battery.
According to the sodium ion battery, by arranging the positive electrode pre-sodium modification material, in the battery charging process, the positive electrode pre-sodium modification additive is irreversibly decomposed to release active sodium ions, active sodium loss caused by the growth of a negative electrode SEI is supplemented, and the effects of improving the energy density and prolonging the cycle life of the sodium ion battery can be achieved. The sodium ion battery anode pre-sodium additive provided by the invention has the advantages of low decomposition potential, high charging specific capacity and irreversible discharge process, and can realize a good in-situ pre-sodium effect of the sodium ion battery. The sodium ion battery positive electrode pre-sodium additive provided by the invention has good air stability, can be compatible with the existing sodium ion battery production process, and has a commercial application prospect.
The features and properties of the present application are described in further detail below with reference to examples:
example 1
Step S1, preparing a pre-sodium material Na of the positive electrode5NbO5。
Weighing Nb2O51g of NaOH and 1.6g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode5NbO5The scanning electron microscope image is shown in fig. 1.
Step S2, detecting the positive electrode pre-sodium material Na5NbO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of Na obtained in step S15NbO5Mixing with 1.5g of carbon black and 1.5g of PVDF, adding 1g of NMP (N-methyl pyrrolidone) to prepare slurry, coating, drying and assembling the battery. Wherein the electrolyte formula is 1M NaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The charge and discharge curves of the battery are shown in FIG. 2 and Table 1, Na5NbO5The charging specific capacity is 409mAh/g, the discharging capacity is less than 10mAh/g, which shows that Na5NbO5The decomposition is irreversible, no back-embedding capacity exists, and the sodium ion battery anode pre-sodiumizing material can be used.
Step S3, detecting sodium vanadium phosphate Na3V2(PO4)3Adding a positive electrode pre-sodium material Na5NbO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
The positive electrode pre-sodium material Na prepared in the step S15NbO5Adding into sodium vanadium phosphate Na3V2(PO4)3The positive electrode material is uniformly mixed, and then the mixture is subjected to size mixing, coating and baking to obtain the sodium iron phosphate added with the positive electrode pre-sodium materialAnd the positive pole piece is matched with the hard carbon to assemble the full battery. The electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. Test for Na5NbO5And when the addition amount of the sodium phosphate is different, the charge and discharge performance of the sodium ion battery is realized, wherein sodium ferric phosphate/hard carbon is used as reference, the test result is shown in table 1, and the contents of sodium vanadium phosphate and hard carbon in each item in table 1 are the same.
TABLE 1
Figure BDA0003291478410000121
Example 2
Step S1, preparing a pre-sodium material Na of the positive electrode3NbO4。
Weighing Nb2O51g of NaOH and 0.95g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode3NbO4。
Step S2, detecting the positive electrode pre-sodium material Na3NbO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 2.
Step S3, detecting sodium vanadium phosphate Na3V2(PO4)3Adding a positive electrode pre-sodium material Na3NbO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S13NbO4Adding into sodium vanadium phosphate Na3V2(PO4)3And uniformly mixing the positive electrode material, then carrying out size mixing, coating and baking to obtain the sodium iron phosphate positive electrode plate added with the positive electrode pre-sodium material, and assembling the positive electrode plate with the hard carbon in a matching manner to form the full battery. ElectrolysisThe formula of the liquid is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. Test for Na3NbO4And when the addition amount is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium sodium phosphate/hard carbon is used as a reference, the test result is shown in table 2, and the contents of the vanadium sodium phosphate and the hard carbon in each item in the table 2 are the same.
TABLE 2
Figure BDA0003291478410000131
Example 3
Step S1, preparing a pre-sodium material Na of the positive electrode5NbO5。
Weighing Nb2O51g of sodium hydroxide, 1.6g of NaOH and 0.2g of glucose, mixing and grinding to obtain mixed powder, and sintering the mixed powder at 900 ℃ for 10 hours in a tubular furnace under nitrogen atmosphere to prepare the carbon-coated Na of the pre-sodium material of the positive electrode5NbO5。
Step S2, detecting the carbon-coated Na of the anode pre-sodium material5NbO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 3.
Step S3, detecting that carbon-coated Na of the positive electrode pre-sodium material is added into sodium vanadium phosphate5NbO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Coating the carbon prepared in the step S1 with Na5NbO5Adding the mixture into a sodium iron phosphate positive electrode material, uniformly mixing, then carrying out size mixing, coating and baking to obtain a sodium iron phosphate positive electrode piece added with a positive electrode pre-sodium material, and assembling the positive electrode piece with hard carbon in a matching manner to form the full-cell. The electrolyte formula is 1M NaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte.Test for Na8Nb2O9And when the addition amount is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium sodium phosphate/hard carbon is used as a reference, the test result is shown in table 3, and the contents of the vanadium sodium phosphate and the hard carbon in each item in the table 3 are the same.
TABLE 3
Figure BDA0003291478410000141
Example 4
Step S1, preparing a pre-sodium material Na of the positive electrode4Nb2O7。
Weighing Nb2O51g of NaOH and 0.64g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode4Nb2O7。
Step S2, detecting the positive electrode pre-sodium material Na4Nb2O7When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 4.
Step S3, detecting the addition of the positive electrode pre-sodium material Na in the vanadium sodium phosphate4Nb2O7When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S14Nb2O7Adding into sodium iron phosphate cathode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene trithiocarbonate was added to the electrolyte. Test for Na4Nb2O7And when the addition amount is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium sodium phosphate/hard carbon is used as a reference, the test result is shown in table 4, and the contents of the vanadium sodium phosphate and the hard carbon in each item in the table 4 are the same.
TABLE 4
Figure BDA0003291478410000151
Figure BDA0003291478410000161
Example 5
Step S1 of preparing the anode pre-sodium material
Weighing Nb2O51g of NaOH and 1.6g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode5NbO5. Collecting 1g of Na5NbO5Mixing with 0.1g of simple substance S, and grinding for 10 minutes to prepare the positive electrode pre-sodium material.
And S2, detecting the charge and discharge performance of the sodium-ion battery when the positive electrode pre-sodium material prepared in the step S1 is used as a positive electrode piece.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 5.
And S3, detecting the charge and discharge performance of the sodium-ion battery when the positive electrode pre-sodium material prepared in the step S1 is added into sodium vanadium phosphate to serve as a positive electrode sheet.
The positive electrode pre-sodium material obtained in step S1 is added to a sodium iron phosphate positive electrode material (Na)3V2(PO4)3) Mixing the above materials uniformly, mixing, coating, and baking to obtain a sodium iron phosphate positive electrode plate containing the positive pre-sodium material, and mixing with hard carbonAnd matching and assembling the whole battery. The electrolyte formula is 1MNaPF6EC/DMC. When the charging and discharging performance of the sodium-ion battery is tested when the pre-sodium material of the positive electrode is added in different amounts, wherein sodium vanadium phosphate/hard carbon is used as a reference, the test results are shown in table 5, and the contents of sodium vanadium phosphate and hard carbon in each item in table 5 are the same.
TABLE 5
Figure BDA0003291478410000171
Example 6
Step S1 of preparing the anode pre-sodium material
Weighing Nb2O51g of NaOH and 1.6g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode5NbO5. Collecting 1g of Na5NbO5Mixing with 0.2g of calcium boride, and grinding for 10 minutes to prepare the positive electrode pre-sodium material.
And S2, detecting the charge and discharge performance of the sodium-ion battery when the positive electrode pre-sodium material prepared in the step S1 is used as a positive electrode piece.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 6.
And S3, detecting the charge and discharge performance of the sodium-ion battery when the positive electrode pre-sodium material prepared in the step S1 is added into sodium vanadium phosphate to serve as a positive electrode sheet.
The positive electrode pre-sodium material obtained in step S1 is added to a sodium iron phosphate positive electrode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1MNaPF6EC/DMC. When the different addition amounts of the pre-sodium material of the anode are testedAnd the charge and discharge performance of the sodium-ion battery, wherein sodium vanadium phosphate/hard carbon is used as reference, the test results are shown in table 6, and the contents of sodium vanadium phosphate and hard carbon in each item in table 6 are the same.
TABLE 6
Figure BDA0003291478410000181
Example 7
Step S1, preparing a pre-sodium material Na of the positive electrode5TaO5。
Weighing Ta2O51g of NaOH and 0.95g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode5TaO5。
Step S2, detecting the positive electrode pre-sodium material Na5TaO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in table 7.
Step S3, detecting the addition of the positive electrode pre-sodium material Na in the vanadium sodium phosphate5TaO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S15TaO5Adding into sodium iron phosphate cathode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1M NaPF6EC/DMC, 2 wt% of ethylene sulfite was added to the electrolyte. Test for Na5TaO5The charging and discharging performance of the sodium-ion battery is realized at different addition amounts, wherein sodium vanadium phosphate/hard carbon is taken as reference, and the test results are shown in tables 7 and 7The contents of vanadium sodium phosphate and hard carbon in the items are the same.
TABLE 7
Figure BDA0003291478410000191
Example 8
Step S1, preparing a pre-sodium material Na of the positive electrode3TaO4。
Weighing Ta2O51g of NaOH and 0.58g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode3TaO4。
Step S2, detecting the positive electrode pre-sodium material Na3TaO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in Table 8.
Step S3, detecting the addition of the positive electrode pre-sodium material Na in the vanadium sodium phosphate3TaO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S15TaO5Adding into sodium iron phosphate cathode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1M NaPF6EC/DMC, 2 wt% of ethylene sulfite was added to the electrolyte. Test for Na5TaO5And when the addition amount of the vanadium phosphate/hard carbon is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium phosphate/hard carbon is used as a reference, the test result is shown in table 8, and the contents of the vanadium phosphate and the hard carbon in each item in the table 8 are the same.
TABLE 8
Figure BDA0003291478410000201
Example 9
Step S1, preparing a pre-sodium material Na of the positive electrode5VO5。
Weighing V2O51g of NaOH and 2.3g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode5VO5。
Step S2, detecting the positive electrode pre-sodium material Na5VO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in Table 9.
Step S3, detecting the addition of the positive electrode pre-sodium material Na in the vanadium sodium phosphate5VO5When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S15VO5Adding into sodium iron phosphate cathode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1M NaPF6EC/DMC, 2 wt% of ethylene sulfite was added to the electrolyte. Test for Na5VO5And when the addition amount of the vanadium phosphate/hard carbon is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium phosphate/hard carbon is used as a reference, the test result is shown in table 9, and the contents of the vanadium phosphate and the hard carbon in each item in the table 9 are the same.
TABLE 9
Figure BDA0003291478410000211
Example 10
Step S1, preparing a pre-sodium material Na of the positive electrode3VO4。
Weighing V2O51g of NaOH and 1.4g of NaOH are mixed and ground to obtain mixed powder, and then the mixed powder is sintered for 10 hours at 900 ℃ to prepare the pre-sodium material Na of the positive electrode3VO4。
Step S2, detecting the positive electrode pre-sodium material Na3VO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
0.7g of the positive electrode pre-sodium modified material prepared in the step S1, 1.5g of carbon black and 1.5g of PVDF are mixed, 1g of NMP (N-methyl pyrrolidone) is added to be mixed into slurry, and the slurry is coated and dried to assemble the battery. Wherein the electrolyte formula is 1MNaPF6EC/DMC, 1 wt% vinylene carbonate was added to the electrolyte. The battery was tested for charge and discharge and the results are shown in Table 10.
Step S3, detecting the addition of the positive electrode pre-sodium material Na in the vanadium sodium phosphate3VO4When the lithium ion battery is used as a positive pole piece, the charge and discharge performance of the sodium ion battery is improved.
Na prepared in step S13VO4Adding into sodium iron phosphate cathode material (Na)3V2(PO4)3) The positive pole piece is mixed evenly, and then the iron phosphate sodium positive pole piece added with the positive pre-sodium material is obtained after size mixing, coating and baking, and is matched with hard carbon to assemble the full cell. The electrolyte formula is 1M NaPF6EC/DMC, 2 wt% of ethylene sulfite was added to the electrolyte. Test for Na3VO4And when the addition amount of the vanadium phosphate/hard carbon is different, the charge and discharge performance of the sodium-ion battery is realized, wherein the vanadium phosphate/hard carbon is used as a reference, the test result is shown in table 10, and the contents of the vanadium phosphate and the hard carbon in each item in the table 10 are the same.
Watch 10
Figure BDA0003291478410000221
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A compound for pre-sodium treatment, characterized in that,
the chemical formula of the compound for pre-sodium treatment is NaxMyOzWherein x is more than or equal to 3 and less than or equal to 7, y is more than or equal to 1 and less than or equal to 2, z is more than or equal to 4 and less than or equal to 7, and M is one or more of Nb, Ta or V.
2. The compound for pre-sodium modification according to claim 1,
the compound for pre-sodium treatment comprises: na (Na)5NbO5、Na3NbO4、Na4Nb2O7、Na5VO5、Na3VO4、Na5TaO5Or Na3TaO4。
3. The compound for pre-sodium treatment according to any one of claims 1 to 2,
the particle size of the compound for pre-sodium treatment is in the range of 10nm-100 μm.
4. A positive electrode pre-sodium treatment material comprising the compound for pre-sodium treatment according to any one of claims 1 to 3.
5. The positive electrode pre-sodium treatment material according to claim 4, further comprising a reducing agent; optionally, the ratio of the reducing agent to the compound for pre-sodium treatment is (1: 100) - (1:1) in terms of mass ratio;
optionally, the reducing agent comprises: at least one of boride, sulfide, phosphide or reducing simple substance;
optionally, the boride comprises: at least one of cobalt boride, molybdenum boride, calcium boride, aluminum boride, magnesium boride, titanium boride, zirconium boride, tungsten boride, or lanthanum boride;
optionally, the sulfide compound comprises: at least one of sodium sulfide, iron sulfide, cobalt sulfide, molybdenum sulfide, tungsten sulfide, titanium sulfide, magnesium sulfide, calcium sulfide, lanthanum sulfide, or tantalum sulfide;
optionally, the phosphide comprises: at least one of iron phosphide, boron phosphide, nickel phosphide, sodium phosphide, or zinc phosphide;
optionally, the reducing element comprises: at least one of elemental sulfur, elemental phosphorus, elemental boron, elemental silicon, elemental aluminum, elemental germanium, elemental arsenic, elemental iodine, elemental vanadium, elemental manganese, elemental iron, elemental cobalt, elemental nickel, or elemental tin.
6. The positive electrode pre-sodium treatment material according to claim 5,
the positive electrode pre-sodium material also comprises a coating layer, and the coating layer is coated on the surface of the compound for pre-sodium treatment; or the coating layer is coated on the surface of the mixture of the compound for pre-sodium treatment and the reducing agent;
wherein the coating layer comprises any one of a carbon coating layer or a conductive polymer coating layer.
7. The method for preparing a compound for pre-sodium treatment according to any one of claims 1 to 3, comprising:
mixing an M source and a sodium source, and sintering at 600-1100 ℃;
wherein when the M source is mixed with the sodium source, the ratio of the metal element M: molar ratio of Na ═ y: [ x (1.2-0.8) ] mixing; the M source comprises at least one of an oxide of the metal M, a carbonate of the metal M, a nitrate of the metal M, a sulfate of the metal M, a chloride of the metal M, a hydroxide of the metal M or an organic compound of the metal M;
the sodium source includes at least one of sodium carbonate, sodium hydroxide, sodium nitrate, sodium chloride, or sodium oxide.
8. The method for preparing the positive electrode pre-sodium treatment material according to any one of claims 4 to 6, characterized by comprising:
mixing the compound for pre-sodium modification according to any one of claims 1 to 3 or the compound for pre-sodium modification prepared by the method for preparing the compound for pre-sodium modification according to claim 7 with a reducing agent; or
Mixing the compound for pre-sodium treatment according to any one of claims 1 to 3 or the compound for pre-sodium treatment prepared by the method for preparing the compound for pre-sodium treatment according to claim 7 with an electrolyte and a reducing additive.
9. A sodium ion battery comprising the positive electrode pre-sodium treatment material according to any one of claims 4 to 6; or the positive electrode pre-sodium material prepared by the method for preparing the positive electrode pre-sodium material according to claim 8.
10. The sodium ion battery of claim 9,
a reducing additive is added into the electrolyte of the sodium ion battery;
optionally, the addition amount of the reducing additive in the electrolyte is 0.01-10% by mass;
optionally, the reducing additive includes at least one of vinylene carbonate, vinylene trithiocarbonate, ethylene sulfite, propane sultone, butane sultone, vinyl sulfate, vinyl sulfite, dimethyl sulfide, dimethyl disulfide, methyl ethyl sulfide, tetrahydrothiophene, or sodium bisoxalate.
CN202111165310.5A 2021-09-30 2021-09-30 Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery Pending CN113896240A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111165310.5A CN113896240A (en) 2021-09-30 2021-09-30 Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111165310.5A CN113896240A (en) 2021-09-30 2021-09-30 Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery

Publications (1)

Publication Number Publication Date
CN113896240A true CN113896240A (en) 2022-01-07

Family

ID=79190039

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111165310.5A Pending CN113896240A (en) 2021-09-30 2021-09-30 Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery

Country Status (1)

Country Link
CN (1) CN113896240A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020637A (en) * 2022-07-05 2022-09-06 湖州超钠新能源科技有限公司 Sodium supplement pole piece, sodium ion battery and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010040311A (en) * 2008-08-05 2010-02-18 Sumitomo Chemical Co Ltd Electrode active material, electrode, and sodium secondary battery
CN109755565A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 Transient metal doped sodium-ion battery positive electrode and its preparation and application
CN111293290A (en) * 2018-12-10 2020-06-16 中南大学 Sodium-rich transition metal oxide composite sodium-supplementing positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in sodium electrovoltaics
CN111834618A (en) * 2020-06-12 2020-10-27 松山湖材料实验室 Carbon-coated lithium supplement material and preparation method and application thereof
JP2020181808A (en) * 2019-04-25 2020-11-05 株式会社日本触媒 Positive electrode and battery provided with the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010040311A (en) * 2008-08-05 2010-02-18 Sumitomo Chemical Co Ltd Electrode active material, electrode, and sodium secondary battery
CN109755565A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 Transient metal doped sodium-ion battery positive electrode and its preparation and application
CN111293290A (en) * 2018-12-10 2020-06-16 中南大学 Sodium-rich transition metal oxide composite sodium-supplementing positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in sodium electrovoltaics
JP2020181808A (en) * 2019-04-25 2020-11-05 株式会社日本触媒 Positive electrode and battery provided with the same
CN111834618A (en) * 2020-06-12 2020-10-27 松山湖材料实验室 Carbon-coated lithium supplement material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020637A (en) * 2022-07-05 2022-09-06 湖州超钠新能源科技有限公司 Sodium supplement pole piece, sodium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
Kong et al. Strategies to solve lithium battery thermal runaway: from mechanism to modification
Hu et al. Promoting reversible redox kinetics by separator architectures based on CoS2/HPGC interlayer as efficient polysulfide‐trapping shield for Li–S batteries
US10205158B2 (en) LMFP cathode materials with improved electrochemical performance
JP6216965B2 (en) Electrode material, electrode plate, lithium ion battery, method for producing electrode material, and method for producing electrode plate
US5512214A (en) Lithium battery electrode compositions
EP3226329B1 (en) Positive electrode active material for nonaqueous electrolyte secondary cell, method for manufacturing same, and nonaqueous electrolyte secondary cell
KR101445692B1 (en) Anode active material for lithium secondary battery and Lithium secondary battery containing the same for anode
CN110783529B (en) Lithium metal cathode for secondary battery and preparation and application thereof
CN108134077B (en) Preparation method of high-voltage lithium ion battery anode material with core-shell structure
KR20100073295A (en) Preparation method of znsb-c composite and anode materials for secondary batteries containing the same composite
CN113620344A (en) Compound for prelithiation and preparation method thereof, positive electrode prelithiation material and preparation method thereof, and lithium battery
Chen et al. Practical evaluation of prelithiation strategies for next‐generation lithium‐ion batteries
KR101219395B1 (en) Anode Material for Lithium Secondary Battery and Manufacturing Method of the Same
KR102220491B1 (en) Positive active materials for rechargable lithium battery, method of preparing the same and rechargable lithium battery using the same
CN113896240A (en) Compound for pre-sodium treatment and preparation method thereof, positive electrode pre-sodium treatment material and preparation method thereof, and sodium ion battery
CN111591971B (en) Titanium lithium phosphate nanocomposite, preparation method and application in aqueous battery
WO2019131129A1 (en) Method for manufacturing positive electrode active material for non-aqueous electrolyte secondary battery
KR101512349B1 (en) Cathode active material for Sodium secondary battery and method for preparing the same
KR101909317B1 (en) Cathode active material for lithium secondary battery and method of making the same
JP2013069567A (en) Electrode active material and method for manufacturing the same, and lithium ion battery
CN116417617B (en) Positive electrode material, positive electrode sheet, sodium ion secondary battery and electricity utilization device
KR102399077B1 (en) Lithium sulfur carbon composite, sulfide-based carbon composite solid electrolyte, cathode and all-solid-state battery using the same
CN114447303A (en) Lithium lanthanum titanate coated graphite negative electrode material and preparation method and application thereof
CN114784283A (en) Coated positive electrode material and preparation method and application thereof
CN115911318A (en) Lithium battery positive electrode active material, lithium battery positive electrode, preparation method of lithium battery positive electrode and lithium battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20221109

Address after: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000

Applicant after: Material Laboratory of Songshan Lake

Applicant after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES

Address before: 523808 building A1, Songshanhu university innovation city, Dongguan City, Guangdong Province

Applicant before: Material Laboratory of Songshan Lake

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20240410

Address after: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000

Applicant after: Material Laboratory of Songshan Lake

Country or region after: China

Applicant after: Songshanhu (Dongguan) Material Technology Development Co.,Ltd.

Address before: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000

Applicant before: Material Laboratory of Songshan Lake

Country or region before: China

Applicant before: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES