CN114790013B - Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof - Google Patents

Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof Download PDF

Info

Publication number
CN114790013B
CN114790013B CN202110105222.XA CN202110105222A CN114790013B CN 114790013 B CN114790013 B CN 114790013B CN 202110105222 A CN202110105222 A CN 202110105222A CN 114790013 B CN114790013 B CN 114790013B
Authority
CN
China
Prior art keywords
sodium
positive electrode
active material
transition metal
equal
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.)
Active
Application number
CN202110105222.XA
Other languages
Chinese (zh)
Other versions
CN114790013A (en
Inventor
胡勇胜
丁飞翔
牛耀申
容晓晖
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.)
Institute of Physics of CAS
Original Assignee
Institute of Physics of CAS
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 Institute of Physics of CAS filed Critical Institute of Physics of CAS
Priority to CN202110105222.XA priority Critical patent/CN114790013B/en
Publication of CN114790013A publication Critical patent/CN114790013A/en
Application granted granted Critical
Publication of CN114790013B publication Critical patent/CN114790013B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
    • C01G53/68—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2 containing rare earth, e.g. La1.62 Sr0.38NiO4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—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

Abstract

The invention relates to a sodium ion battery positive electrode active material of self-supplementing sodium, a preparation method and application thereof, wherein the sodium ion battery positive electrode active material of self-supplementing sodium is a sodium-rich manganese-based layered oxide material, and the chemical general formula is as follows: na (Na) x Ni a Cu b Fe c Mn d M e 0 2±δ The method comprises the steps of carrying out a first treatment on the surface of the Wherein Ni, cu, fe, mn is a transition metal element, M is an ion for doping substitution to the transition metal site; mn ions are in a positive trivalent or mixed valence state of positive trivalent and positive tetravalent; in the structure of the sodium-rich manganese-based layered oxide material, ions of transition metal sites form an octahedral structure with six adjacent oxygens, and NaO coordinated with the octahedrons 6 The layers are alternately arranged to form the O3-type sodium-rich manganese-based layered oxide material with the space group of R-3 m; mn in low voltage region during first cycle charging 3+ /Mn 4+ Oxidation is accompanied with the removal of sodium ions to effectively compensate the first week negativeActive sodium ions consumed in the process of forming SEI film extremely, and Mn is suppressed in the discharge process control voltage range 4+ Reduction reduces the generation of the ginger taylor effect and significantly improves the battery cycle performance.

Description

Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a self-supplementing sodium ion battery anode active material, a preparation method and application thereof.
Background
Sodium ion batteries have a great application potential in a fixed power grid storage system due to the characteristics of low cost, abundant sources and the like, so that the sodium ion batteries are widely paid attention to. Based on sodium ion layered oxide Na x TMO 2 Various prototype batteries have been developed in which (x.ltoreq.1, tm is a transition metal ion), a polyanion compound and a prussian blue analog are used as the positive electrode and hard carbon is used as the negative electrode. Although each of these advanced positive/negative electrode materials achieves higher power and energy density, further increases in full cell energy density are limited in full cells due to irreversible loss of sodium by the Solid Electrolyte Interface (SEI) formed on the negative side.
In response to this problem, several methods of pre-sodium modification have been explored by current reports to introduce additional sodium sources into the battery system.
1) And (3) carrying out electrochemical pre-sodiumization on the negative electrode, assembling a half cell on the negative electrode, carrying out electrochemical pre-cycling to enable the negative electrode to form SEI in advance, and then disassembling the cell to take out the pre-sodiumized negative electrode to be matched with the positive electrode again to assemble the full cell. Although this approach significantly improves the first week coulombic efficiency, energy density, and subsequent cycling stability of the battery system, the complex process of operation presents challenges for practical applications.
2) Direct mixed contact of the anode material with sodium metal also appears to be an effective pre-sodium strategy, as there have been reports of successful incorporation of stable lithium metal powder into graphite and silicon anodes for pre-lithiation. However, na metal is more reactive than Li metal and sensitive to ambient atmosphere/dry air, which suggests that these composite electrodes are not conducive to scale-up or require costly manufacturing processes.
3) Positive pre-sodium modification is another way to compensate for the irreversible capacity loss of the negative electrode. The introduction of a sacrificial sodium-rich salt with an appropriate electrochemical decomposition voltage and chemical stability as an additive to the positive side can effectively offset the initial sodium loss. However, previous studies have shown that sodium ions in the additive are released to produce byproducts, such as N 2 CO or CO 2 And create voids in the passivation layer of the composite positive or negative electrode, which is absolutely undesirable for the battery.
Thus, in order to further increase the energy density of sodium ion batteries, another novel sodium compensation strategy is needed that needs to be compatible with existing industrial battery manufacturing processes and introduce little by-product.
Disclosure of Invention
The embodiment of the invention provides a self-supplementing sodium positive electrode active material of a sodium ion battery, and a preparation method and application thereof.
In a first aspect, an embodiment of the present invention provides a sodium-ion battery positive electrode active material for self-replenishing sodium, where the sodium-ion battery positive electrode active material for self-replenishing sodium is a sodium-manganese-rich layered oxide material, and has a chemical general formula: na (Na) x Ni a Cu b Fe c Mn d M e 0 2±δ ；
Wherein Ni, cu, fe, mn is a transition metal element, M is an ion for doping substitution to the transition metal site; mn ions are in a positive trivalent or mixed valence state of positive trivalent and positive tetravalent; in the structure of the sodium-rich manganese-based layered oxide material, ions of transition metal sites form an octahedral structure with six adjacent oxygens, and NaO coordinated with the octahedrons 6 The layers are alternately arranged to form the O3-type sodium-rich manganese-based layered oxide material with the space group of R-3 m;
the M specifically comprises Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4 + 、Nb 5+ One or more of the following;x, a, b, c, d, e and 2+ -delta are the mole numbers of the corresponding elements respectively, wherein each component in the chemical general formula satisfies charge conservation and stoichiometric conservation, wherein x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.35,0, c is more than or equal to 0 and less than or equal to 0.35,0 and less than or equal to 0.35,0.1 and less than or equal to 0.6,0, e is more than or equal to 0.35,0 and delta is less than or equal to 0.1, and a, b and c are not 0 at the same time.
In a second aspect, an embodiment of the present invention provides a method for preparing the positive electrode active material of a sodium ion battery for self-supplementing sodium according to the first aspect, where the preparation method is a solid phase method, and includes:
mixing a sodium source with the stoichiometric amount of 100-105 wt% of sodium and an oxide, hydroxide or nitrate with the stoichiometric amount of nickel, copper, iron, manganese and M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder; the sodium source comprises one or more of sodium carbonate, sodium nitrate, sodium peroxide, sodium superoxide, sodium hydroxide and sodium oxalate;
tabletting the obtained precursor powder, placing the precursor powder into a crucible, calcining for 10-24 hours at 700-900 ℃ in a sintering atmosphere of air or oxygen, rapidly cooling to room temperature in 1-300 s, and grinding to obtain the sodium ion battery anode active material;
wherein M is an element substituted by doping transition metal, and specifically comprises Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following.
In a third aspect, an embodiment of the present invention provides a method for preparing the positive electrode active material of a sodium ion battery with self-supplementing sodium according to the first aspect, where the preparation method is a coprecipitation-high temperature solid phase method, and includes:
preparing a mixed solution of water-soluble Ni salt, cu salt, fe salt, mn salt and M salt according to the required proportion of Ni, cu, fe, mn and M as a first solution; wherein the concentration of cations in the first solution is 1-3mol/L; m is an element substituted by doping transition metal, and specifically comprises Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following;
dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
simultaneously adding the first solution and the second solution into a reaction vessel in the stirring process, and performing coprecipitation reaction at 50-60 ℃, wherein the pH value is maintained at 10-12 in the reaction process;
aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a uniformly distributed hydroxide precursor of the transition metal element;
uniformly mixing the hydroxide precursor with a sodium source with the stoichiometric amount of 100-105 wt% of sodium, preserving heat for 3-6 hours at 400-500 ℃ in an air atmosphere, calcining for 10-24 hours at 700-900 ℃, rapidly cooling to room temperature within 1-300 s, and grinding to obtain the sodium ion battery anode active material; wherein the sodium source comprises: sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
In a fourth aspect, an embodiment of the present invention provides a method for preparing the positive active material of a sodium ion battery with self-replenishing sodium according to the first aspect, which is a sol-gel method, including:
weighing 100-105 wt% of sodium ions, soluble salts of transition metal ions and a proper amount of citric acid in stoichiometric ratio to form slurry of mixed solution; wherein the transition metal ions comprise Ni, cu, fe, mn; the transition metal ion also comprises an element M which is doped and substituted on the transition metal position; m specifically includes Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following;
heating and evaporating the obtained slurry in an oil bath pan to dryness to form xerogel;
and (3) placing the obtained xerogel in a crucible, preprocessing for 3-6 hours at 400-500 ℃, grinding the preprocessed powder, tabletting, placing the obtained powder in the crucible, calcining for 10-24 hours at 700-900 ℃ in air or oxygen atmosphere, rapidly cooling to room temperature within 1-300 seconds, and grinding to obtain the sodium ion battery anode active material.
In a fifth aspect, an embodiment of the present invention provides an electrode material for a sodium ion secondary battery, including: a conductive additive, a binder and the sodium ion battery positive electrode active material of the self-replenishing sodium of the first aspect.
Preferably, the conductive additive includes: carbon black, acetylene black, graphite powder, carbon nanotubes, graphene, nitrogen-doped carbon;
the binder comprises one or more of polyvinylidene fluoride PVDF, sodium alginate, sodium carboxymethyl cellulose CMC and styrene butadiene rubber SBR.
In a sixth aspect, an embodiment of the present invention provides a positive electrode sheet including the electrode material of the sodium ion secondary battery described in the fifth aspect.
In a seventh aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode sheet according to the sixth aspect.
The sodium ion battery positive electrode active material with self-supplementing sodium provided by the embodiment of the invention introduces a large amount of trivalent manganese ions into the material through composition optimization design, and leads Mn to be processed through quenching treatment 3+ Ion and Na + While remaining in the bulk of the material. The self-supplementing sodium-ion battery anode active material has the following advantages: 1) The inclusion of more sodium ions in the bulk phase can compensate for sodium ions consumed by the formation of a negative Solid Electrolyte Interface (SEI) film and reduce the formation of surface alkaline sodium carbonate; 2) Mn of low oxidation plateau 3+ Can provide charge compensation for the removal of sodium ions, avoid the consumption of other active ions, obviously reduce the material cost and improve the energy density of the system.
The sodium ion full battery constructed by the positive electrode matched with the hard carbon negative electrode has the characteristics of high average energy storage voltage, high energy density and high power density, can be used as a green clean energy source for power generation, intelligent power grid peak shaving, a distributed power station, a backup power supply, a communication base station or energy storage equipment of a low-speed electric automobile and the like, and has excellent safety performance, multiplying power performance and cycle performance.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is an X-ray diffraction (XRD) pattern of a sodium-rich manganese-based layered oxide positive electrode material prepared in accordance with an embodiment of the present invention, which is self-replenishing, and a conventional manganese-based oxide positive electrode material of a comparative example;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a self-replenishing sodium-rich manganese-based layered oxide cathode material prepared in example 4 of the present invention;
FIG. 3 is an SEM image of a self-replenishing sodium-rich manganese-based layered oxide cathode material prepared in example 6 of the present invention;
FIG. 4 is an SEM image of a conventional manganese-based oxide positive electrode material prepared according to a comparative example of the present invention;
FIG. 5 is a graph showing the charge and discharge of a half cell of a sodium-rich manganese-based layered oxide cathode material prepared in example 4 of the present invention two weeks before testing;
FIG. 6 is a graph showing the charge and discharge curves of a half cell of a sodium-rich manganese-based layered oxide positive electrode material prepared in example 5 of the present invention for the first two weeks;
FIG. 7 is a graph showing the charge and discharge curves of a half cell of a sodium-rich manganese-based layered oxide positive electrode material prepared in example 6 of the present invention for the first two weeks;
FIG. 8 is a graph showing charge and discharge curves two weeks before half-cell testing of a conventional manganese-based oxide cathode material prepared using a comparative example of the present invention;
FIG. 9 is a graph showing the charge and discharge curves of the sodium-rich manganese-based layered oxide positive electrode material prepared in example 6 of the present invention and the conventional manganese-based oxide positive electrode material prepared in comparative example, respectively, with a hard carbon negative electrode during the first two weeks of a full cell;
fig. 10 is a graph showing cycle performance of a full cell of a hard carbon negative electrode and a sodium-rich manganese-based layered oxide positive electrode material prepared by using the self-replenishing sodium prepared in example 6 of the present invention and a conventional manganese-based oxide positive electrode material prepared in comparative example, respectively.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The self-supplementing sodium-ion battery anode active material is a sodium-rich manganese-based layered oxide material, and has a chemical general formula: na (Na) x Ni a Cu b Fe c Mn d M e 0 2±δ The method comprises the steps of carrying out a first treatment on the surface of the Wherein Ni, cu, fe, mn is a transition metal element, M is an ion for doping substitution to the transition metal site; mn ions are in a positive trivalent or mixed valence state of positive trivalent and positive tetravalent; in the structure of the sodium-rich manganese-based layered oxide material, ions of transition metal sites form an octahedral structure with six adjacent oxygens, and NaO coordinated with the octahedrons 6 The layers are alternately arranged to form the O3-type sodium-rich manganese-based layered oxide material with the space group of R-3 m;
m specifically includes Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following; x, a, b, c, d, e and 2+ -delta are the mole numbers of the corresponding elements respectively, wherein each component in the chemical general formula satisfies charge conservation and stoichiometric conservation, wherein x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.35,0, c is more than or equal to 0 and less than or equal to 0.35,0 and less than or equal to 0.35,0.1 and less than or equal to 0.6,0, e is more than or equal to 0.35,0 and delta is less than or equal to 0.1, and a, b and c are not 0 at the same time.
The sodium-ion battery sodium-manganese-rich layered oxide material can be used for the positive electrode activity of a sodium-ion secondary batteryA sexual material. Introducing a large amount of trivalent manganese ions into the material through composition optimization design, and quenching Mn 3+ Ion and Na + While remaining in the bulk of the material. The material has the following advantages: 1) The bulk phase contains more sodium ions, so that sodium ions consumed by formation of negative electrode SEI can be compensated, and formation of surface alkaline sodium carbonate is reduced; 2) Mn of low oxidation plateau 3+ Can provide charge compensation for the removal of sodium ions, avoid the consumption of other active ions, obviously reduce the material cost and improve the energy density of the system. The sodium ion full battery constructed by the positive electrode matched with the hard carbon negative electrode has the characteristics of high average energy storage voltage, high energy density and high power density. The sodium ion full battery constructed by the positive electrode matched with the hard carbon negative electrode has the characteristics of high average energy storage voltage, high energy density and high power density, can be used as a green clean energy source for power generation, intelligent power grid peak shaving, a distributed power station, a backup power supply, a communication base station or energy storage equipment of a low-speed electric automobile and the like, and has excellent safety performance, multiplying power performance and cycle performance.
The embodiment of the invention also provides a preparation method of the sodium-manganese-rich layered oxide positive electrode material used as the positive electrode active material of the sodium ion battery for self-supplementing sodium, which can be specifically prepared by a solid phase method, a coprecipitation-high temperature solid phase method or a sol-gel method.
The preparation method by adopting the solid phase method specifically comprises the following steps:
step 110, mixing a sodium source with the required sodium stoichiometry of 100-105 wt%, an oxide of nickel, an oxide of copper, an oxide of iron, an oxide of manganese and an oxide, hydroxide or nitrate of M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder;
wherein the sodium source comprises one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate; m is as described above and will not be described in detail.
And 120, tabletting the obtained precursor powder, placing the precursor powder into a crucible, calcining for 10-24 hours at 700-900 ℃ in a sintering atmosphere of air or oxygen, rapidly cooling to room temperature within 1-300 s, and grinding to obtain the sodium-manganese-rich basal layer oxide cathode material.
The preparation method by adopting the coprecipitation-high temperature solid phase method specifically comprises the following steps:
step 210, preparing a mixed solution of water-soluble Ni salt, cu salt, fe salt, mn salt and M salt according to the required proportion of Ni, cu, fe, mn and M as a first solution; wherein the concentration of cations in the first solution is 1-3mol/L;
wherein M is as described above and will not be described again.
Step 220, dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
step 230, adding the first solution and the second solution into a reaction vessel simultaneously in the stirring process, and performing coprecipitation reaction at 50-60 ℃, wherein the pH value is maintained to be 10-12 in the reaction process;
step 240, aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a uniformly distributed hydroxide precursor of the transition metal element;
step 250, uniformly mixing a hydroxide precursor and a sodium source with the sodium content of 100-105 wt% in stoichiometric amount, preserving heat for 3-6 hours at 400-500 ℃ in air atmosphere, calcining for 10-24 hours at 700-900 ℃, rapidly cooling to room temperature within 1-300 s, and grinding to obtain the sodium-manganese-rich basal layer oxide anode material;
wherein the sodium source comprises: sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
The method adopting the sol-gel method for preparation comprises the following steps:
step 310, weighing 100-105 wt% of sodium ions, soluble salts of transition metal ions and a proper amount of citric acid according to the required stoichiometric ratio, and dissolving the sodium ions, the soluble salts of transition metal ions and a proper amount of citric acid into deionized water to form slurry of a mixed solution; wherein the transition metal ions comprise Ni, cu, fe, mn;
wherein the transition metal ion also comprises an element M which is doped and substituted for the transition metal position; m is as described above and will not be described in detail.
Step 320, heating and evaporating the obtained slurry in an oil bath to dryness to form xerogel;
330, placing the obtained xerogel in a crucible, preprocessing for 3-6 hours at 400-500 ℃, grinding the preprocessed powder, tabletting, placing in the crucible, calcining for 10-24 hours at 700-900 ℃ in air or oxygen atmosphere, rapidly cooling to room temperature within 1s-300s, and grinding to obtain the sodium-manganese-rich basal layer oxide positive electrode material.
The preparation methods adopt a rapid cooling method after high-temperature calcination, and can comprise the following steps: 1) Rapidly placing the high-temperature sample obtained by calcination in liquid nitrogen; 2) Rapidly placing the high-temperature sample obtained by calcination between two clean metal plates with high specific heat capacity (> 0.1 KJ/Kg); 3) The high temperature sample obtained by calcination was rapidly placed in a metal tank filled with argon. Of course, the method is not limited to the above methods, and other methods which are mature in the prior art and can rapidly reduce the temperature of the material can be adopted.
The preparation method provided by the invention effectively maintains Mn to be designed Mn through the quenching process with accurate control 3+ Valence or Mn 3+ /Mn 4+ In a mixed valence state, the material is used for matching a full battery with a negative electrode plate, and Mn in a low-voltage region in a first-cycle charging process 3+ /Mn 4+ Active sodium ions consumed in the process of forming SEI film on the first-week cathode can be effectively compensated by oxidation accompanied with sodium ion release, and Mn is inhibited by controlling voltage range in the discharging process 4+ Reduction reduces the generation of the ginger taylor effect and significantly improves the battery cycle performance. The self-replenishing sodium positive electrode material is applied to sodium ion batteries, is simple to operate, does not need to adjust the existing battery production process, can effectively compensate active sodium ion loss caused by some irreversible reactions in a full battery system, and further remarkably improves the energy density of the full battery.
In order to better understand the technical scheme provided by the invention, the self-replenishing sodium-ion battery positive electrode active material-sodium-rich manganese-based layered oxide material, the preparation method and the performance thereof are further detailed below by combining some specific examples.
Example 1
In the embodiment, the sodium-rich manganese-based layered oxide anode material NaNi with self-supplementing sodium is prepared by adopting a coprecipitation-high temperature solid phase method 0.3 Fe 0.2 Mn 0.5 O 2 The method comprises the following specific steps of:
NaNi according to the molecular formula 0.3 Fe 0.20 Mn 0.5 O 2 NiSO is prepared by the proportion of Ni, fe and Mn 4 ·6H 2 O，FeSO 4 ·7H 2 O and MnSO 4 ·H 2 O deionized water solution with the concentration of 2mol/L is prepared;
preparing alkali liquor by using sodium hydroxide, ammonia water and deionized water, wherein the concentration of the sodium hydroxide is 4mol/L and the concentration of the ammonia is 1mol/L;
adding a proper amount of deionized water into a reaction kettle, introducing nitrogen, heating to 60 ℃ and preserving heat, then adding sodium hydroxide and ammonia water into the reaction kettle to adjust the pH value to 11.7, stirring at a speed of 500r/min, and then simultaneously dropwise adding a transition metal solution and alkali liquor, and maintaining the pH value to about 11.7;
after the reaction is finished, filtering and washing the precipitate until the pH value of the filtered water is less than or equal to 9.5, and drying the precipitate at 120 ℃ for 12 hours to obtain a uniformly distributed hydroxide precursor of the transition metal element;
uniformly mixing the obtained hydroxide precursor and excessive sodium carbonate with 2% of excessive sodium carbonate according to stoichiometric ratio, preserving heat at 450 ℃ for 5 hours under air atmosphere, calcining at 850 ℃ for 15 hours, rapidly placing a sample at high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide anode material NaNi for sodium supplementation 0.3 Fe 0.2 Mn 0.5 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m.
Example 2
In the embodiment, a solid phase method is adopted to prepare a sodium-rich manganese-based layered oxide anode material NaNi for self-supplementing sodium 0.3 Fe 0.2 Mn 0.5 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, fe 2 O 3 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide anode material NaNi for sodium supplementation 0.3 Fe 0.2 Mn 0.5 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m.
Example 3
In the embodiment, a solid phase method is adopted to prepare a sodium-rich manganese-based layered oxide anode material NaNi for self-supplementing sodium 0.2 Cu 0.1 Fe 0.20 Mn 0.50 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, cuO, fe 2 O 3 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide anode material NaNi for sodium supplementation 0.2 Cu 0.1 Fe 0.20 Mn 0.50 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide cathode material with self-supplementing sodium prepared in this example is shown in FIG. 1, and the comparison standard card shows that the main phase is O3 phase, the space group is R-3m, and the material contains a small amount of copper oxide impurity phase.
Example 4
In the embodiment, the sodium-rich manganese-based layered oxide anode material Na for self-supplementing sodium is prepared by adopting a solid phase method 0.9 Cu 0.22 Fe 0.30 Mn 0.48 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess of 2%), cuO, fe 2 O 3 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide positive electrode material Na for sodium supplementation 0.9 Cu 0.22 Fe 0.30 Mn 0.48 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide cathode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the main phase of the XRD pattern is an O3 phase and the space group is R-3m as shown in a comparison standard card. As shown in fig. 2, the SEM image shows good crystallinity with a particle size of about 4 μm.
Example 5
In the embodiment, the sodium-rich manganese-based layered oxide anode material Na for self-supplementing sodium is prepared by adopting a solid phase method 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.48 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, cuO, fe 2 O 3 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide positive electrode material Na for sodium supplementation 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.48 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m.
Example 6
In this example, a solid phase method is used to prepare a sodium-rich manganese-based layered oxide with self-supplementing sodiumPositive electrode material Na 0.9 Ni 0.11 Cu 0.1 1 Fe 0.30 Mn 0.38 Ti 0.10 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, cuO, fe 2 O 3 、TiO 2 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide positive electrode material Na for sodium supplementation 0. 9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.38 Ti 0.10 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m. As shown in fig. 3, the SEM image shows good crystallinity with a particle size of about 2 μm.
Example 7
In the embodiment, the sodium-rich manganese-based layered oxide anode material Na for self-supplementing sodium is prepared by adopting a solid phase method 0.9 Ni 0.11 Cu 0.1 1 Fe 0.30 Mn 0.28 Ti 0.20 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess of 2%), cuO, fe 2 O 3 、TiO 2 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at a high temperature between two copper plates, cooling, and cooling to room temperature to obtain the sodium-rich manganese-based layered oxide positive electrode material Na for sodium supplementation 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.28 Ti 0.20 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m.
Example 8
In the embodiment, the sodium-rich manganese-based layered oxide anode material Na for self-supplementing sodium is prepared by adopting a solid phase method 0.9 Ni 0.11 Cu 0.1 1 Fe 0.30 Mn 0.0.38 Ti 0.10 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, cuO, fe 2 O 3 、TiO 2 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, rapidly placing a sample at high temperature into liquid nitrogen for cooling, and volatilizing the liquid nitrogen to obtain the sodium-rich manganese-based layered oxide anode material Na for sodium supplementation 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.0.38 Ti 0.10 O 2 。
The XRD pattern of the sodium-rich manganese-based layered oxide positive electrode material with self-supplementing sodium prepared in the embodiment is shown in figure 1, and the comparison standard card can be known to be a pure O3 phase substance, and the space group is R-3m.
Example 9
The embodiment adopts a sol-gel method to prepare the Na-rich manganese-based layered oxide anode material Na with self-supplementing sodium 0.9 Cu 0.11 Ni 0.11 Fe 0.30 Mn 0.48 O 2 The method comprises the following specific steps of:
weighing sodium nitrate, manganese acetate, nickel acetate, copper acetate, ferric nitrate and a proper amount of citric acid according to a required stoichiometric ratio, and dissolving the sodium nitrate, the manganese acetate, the nickel acetate, the copper acetate, the ferric nitrate and a proper amount of citric acid into deionized water to form a mixed solution; heating and evaporating the obtained slurry in an oil bath pan to dryness to form xerogel; collecting the obtained xerogel, placing in a crucible, pre-treating at 450deg.C for 3-6 hr, grinding the pre-treated powder, tabletting, placing in the crucible, calcining at 800deg.C for 20 hr under air as sintering atmosphere, rapidly placing sample between two copper plates, cooling, and cooling to room temperature to obtain sodium-rich manganese-based lamellar oxygen for supplementing sodiumPositive electrode material Na of chemical compound 0.9 Cu 0.11 Ni 0.11 Fe 0.30 Mn 0.48 O 2 。
Comparative example
In this example, a solid phase method was used to prepare a conventional manganese-based layered oxide positive electrode material Na 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.38 Ti 0.10 O 2 The method comprises the following specific steps of: weighing Na according to stoichiometric ratio 2 CO 3 (excess 2%), niO, cuO, fe 2 O 3 、TiO 2 And Mn of 2 O 3 Adding a proper amount of absolute ethyl alcohol into an agate mortar, mixing and grinding uniformly to obtain a precursor, pressing the precursor into a wafer with the diameter of 15mm under the pressure of 10Mpa, treating for 15 hours at the temperature of 900 ℃ in an air atmosphere, cooling along with a furnace and cooling to room temperature to obtain the conventional manganese-based layered oxide anode material Na 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.38 Ti 0.10 O 2 。
The XRD pattern of the conventional manganese-based layered oxide cathode material prepared in this example is shown in FIG. 1, and the comparison standard card shows that the conventional manganese-based layered oxide cathode material is a pure O3 phase substance, and the space group is R-3m. SEM pictures are shown in fig. 4, with particle size of about 2 microns and a rough surface.
Further studies have found that the surface-coated amorphous material is sodium carbonate, indicating that sodium ions in the bulk phase of the particles slowly leach out during the material cool down process to form amorphous sodium carbonate with concomitant oxidation of bulk manganese ions.
The sodium-rich manganese-based layered oxide cathode materials of the present invention, which were self-replenishing sodium, prepared in the above-described respective examples, and the materials of the comparative examples were tested.
And (3) half-cell assembly: the sodium-rich manganese-based layered oxide cathode material of each example was subjected to sodium self-supplementation with conductive carbon black (Super P) and vinylidene fluoride (PVDF) in a mass ratio of 75:15:10 pulping in N-methylpyrrolidone (NMP) solution, coating on aluminum foil, vacuum drying, cutting into 12mm diameter pole pieces (carrying about 5-10 mg/cm) 2 ) NaClO with metal sodium sheet as negative electrode and 1mol/L 4 Polycarbonate (PC): ethylene Carbonate (EC): dimethyl carbonate (DMC) (volume ratio 1:1:1) solution is used as electrolyte, a glass fiber diaphragm is used for assembling the CR2032 button cell half cell in an argon glove box. The pole piece is matched with a hard carbon negative electrode, and can be assembled into a full battery, wherein the first effect of the hard carbon is 80%, and the reversible specific capacity is 350 mAh.g -1 。
And (3) charge and discharge testing: the voltage range of the charge and discharge of the button half cell is 2.5-4.0V, the voltage range of the full cell is 1.0-4.0V, the activation is carried out twice by adopting a small current density of 15mA/g (0.1C) before the cyclic test, then the cyclic test is carried out by adopting the cyclic test under the 1C multiplying power in the same voltage range, and all electrochemical performance tests are carried out at room temperature.
FIG. 5 is a self-replenishing Na-Mn-rich layered oxide cathode material Na prepared in example 4 0.9 Cu 0.22 Fe 0.30 Mn 0.48 O 2 The first 2 weeks of charge and discharge curve of (2) can find about 2.5V voltage platform in the first week of charge process, and the platform is mainly composed of Mn in the material body 3+ Oxidation and concomitant extraction of sodium ions. Although Mn 4+ /Mn 3 + The redox process is reversible, but the plateau voltage is too low (matching hard carbon results in a wider charge-discharge interval), and Mn 3+ The resulting ginger taylor effect deteriorates the structural stability of the material. Therefore, manganese ions can be stabilized in positive quadrivalent state only through first-week charging, and the released sodium ions are used for compensating the consumption of active sodium ions by SEI formed in the first week of the negative electrode to reach the effect of self-supplementing sodium, so that the consumption of a full-battery system to a positive electrode material is reduced, and the overall energy density is remarkably improved. The first-week charge specific capacity of the positive electrode material is 129 mAh.g -1 Reversible specific capacity of 97 mAh.g -1 。
FIG. 6 is a self-replenishing Na-Mn-rich layered oxide cathode material Na prepared in example 5 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.48 O 2 The first-week charge-discharge curve of (2) is 130 mAh.g in the voltage range of 2.5-4.0V -1 Reversible specific capacity of 100 mAh.g -1 。
FIG. 7 is an embodiment6, the prepared sodium-enriched manganese-based layered oxide positive electrode material Na with self-supplementing sodium 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.38 Ti 0.10 O 2 The first-week charge-discharge curve of (2) is 133 mAh.g in the voltage range of 2.5-4.0V -1 Reversible specific capacity 106 mAh.g -1 。
FIG. 8 is a comparative example of a conventional manganese-based layered oxide positive electrode material Na 0.9 Ni 0.11 Cu 0.11 Fe 0.30 Mn 0.38 Ti 0.10 O 2 The first-week charge-discharge curve of (2) is 124 mAh.g in the voltage range of 2.5-4.0V -1 Wherein Mn at low voltage is remarkably absent 3+ Oxidation platform with reversible specific capacity of 99 mAh.g -1 。
Fig. 9 is a first-week charge-discharge curve of a full battery using the self-replenishing sodium-rich manganese-based layered oxide positive electrode material prepared in example 6 of the present invention and the conventional manganese-based oxide positive electrode material prepared in comparative example, respectively, matched with a hard carbon negative electrode. It can be seen that the lower voltage plateau in the charging process of the embodiment is mainly composed of Mn 3+ Oxidation was provided without the platform in the comparative example. The reversible specific capacity of the positive electrode system with the self-sodium supplementing effect is remarkably improved (mAh.g.) -1 90 mAh.g higher than conventional manganese-based materials -1 ). It can also be seen from fig. 10 that a material-matched full cell with self-replenishing sodium also achieves more excellent cycling performance.
The sodium ion battery positive electrode active material with self-supplementing sodium provided by the invention introduces a large amount of trivalent manganese ions into the material through composition optimization design, and leads Mn to be processed through quenching treatment 3+ Ion and Na + While remaining in the bulk of the material. The carrier phase of the material contains more sodium ions, so that the sodium ions consumed by the formation of negative electrode SEI can be compensated, the formation of surface alkaline sodium carbonate is reduced, and meanwhile, the Mn of a platform is reduced 3+ Can provide charge compensation for the removal of sodium ions, avoid the consumption of other active ions, obviously reduce the material cost and improve the energy density of the system. Sodium ion full battery constructed by adopting positive electrode matched with hard carbon negative electrode and having average energy storage voltageThe energy storage device has the characteristics of high energy density and high power density, can be used as a green clean energy source for power generation, intelligent power grid peak shaving, distribution power stations, backup power sources, communication base stations or low-speed electric automobiles and the like, and has excellent safety performance, multiplying power performance and cycle performance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (8)

1. The sodium ion battery positive electrode active material is characterized in that the sodium ion battery positive electrode active material is a sodium-rich manganese-based layered oxide material, and has a chemical formula as follows: na (Na) x Ni a Cu b Fe c Mn d M e 0 2±δ ；
Wherein Ni, cu, fe, mn is a transition metal element, M is an ion for doping substitution to the transition metal site; mn ions are in a positive trivalent or mixed valence state of positive trivalent and positive tetravalent; in the structure of the sodium-rich manganese-based layered oxide material, ions of transition metal sites form an octahedral structure with six adjacent oxygens, and NaO coordinated with the octahedrons 6 The layers are alternately arranged to form the O3-type sodium-rich manganese-based layered oxide material with the space group of R-3 m; firstly, a positive electrode active material precursor is obtained, and then the positive electrode active material precursor is calcined at high temperature and then immediately quenched to lead Mn to be obtained 3+ And Na (Na) + While remaining in the sodium-rich manganese-based layered oxide material phase;
the M specifically comprises Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One of (a)One or more species; x, a, b, c, d, e and 2+ -delta are the mole numbers of the corresponding elements respectively, wherein each component in the chemical general formula satisfies charge conservation and stoichiometric conservation, wherein x is more than or equal to 0.67 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.35,0, c is more than or equal to 0 and less than or equal to 0.35,0 and less than or equal to 0.35,0.1 and less than or equal to 0.6,0, e is more than or equal to 0.35,0 and delta is less than or equal to 0.1, and a, b and c are not 0 at the same time.
2. A method for preparing a sodium ion battery positive electrode active material of self-supplementing sodium according to claim 1, wherein the preparation method is a solid phase method and comprises the following steps:
mixing a sodium source with the stoichiometric amount of 100-105 wt% of sodium and an oxide, hydroxide or nitrate with the stoichiometric amount of nickel, copper, iron, manganese and M according to a proportion, adding absolute ethyl alcohol or acetone, and grinding uniformly to obtain precursor powder; the sodium source comprises one or more of sodium carbonate, sodium nitrate, sodium peroxide, sodium superoxide, sodium hydroxide and sodium oxalate;
tabletting the obtained precursor powder, placing the precursor powder into a crucible, calcining for 10-24 hours at 700-900 ℃ in a sintering atmosphere of air or oxygen, rapidly cooling to room temperature in 1-300 s, and grinding to obtain the sodium ion battery anode active material;
wherein M is an element substituted by doping transition metal, and specifically comprises Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following.
3. The method for preparing the positive electrode active material of the sodium ion battery with self-supplementing sodium as claimed in claim 1, wherein the preparation method is a coprecipitation-high temperature solid phase method, and comprises the following steps:
preparing a mixed solution of water-soluble Ni salt, cu salt, fe salt, mn salt and M salt according to the required proportion of Ni, cu, fe, mn and M as a first solution; wherein the concentration of cations in the first solution is 1-3mol/L; m is a transition metalThe generic site is doped with substituted elements, specifically comprising Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following;
dissolving NaOH or KOH in deionized water with the concentration of 2-4mol/L, and adding a proper amount of ammonia water to form a second solution;
simultaneously adding the first solution and the second solution into a reaction vessel in the stirring process, and performing coprecipitation reaction at 50-60 ℃, wherein the pH value is maintained at 10-12 in the reaction process;
aging for 0-24 hours after the coprecipitation reaction is finished, filtering the precipitate, washing and drying to obtain a uniformly distributed hydroxide precursor of the transition metal element;
uniformly mixing the hydroxide precursor with a sodium source with the stoichiometric amount of 100wt% -105wt% of sodium, preserving heat for 3-6 hours at 400-500 ℃ in an air atmosphere, calcining for 10-24 hours at 700-900 ℃, rapidly cooling to room temperature within 1s-300s, and grinding to obtain the sodium ion battery anode active material; wherein the sodium source comprises: sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate.
4. The method for preparing the positive electrode active material of the sodium ion battery with self-supplementing sodium as claimed in claim 1, wherein the preparation method is a sol-gel method and comprises the following steps:
weighing 100wt% -105wt% of sodium ions, soluble salts of transition metal ions and a proper amount of citric acid according to the required stoichiometric ratio, and dissolving the sodium ions, the soluble salts of transition metal ions and a proper amount of citric acid into deionized water to form slurry of a mixed solution; wherein the transition metal ions comprise Ni, cu, fe, mn; the transition metal ion also comprises an element M which is doped and substituted on the transition metal position; m specifically includes Li + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、B 3+ 、Co 3+ 、V 3+ 、Y 3+ 、Ti 4+ 、Zr 4+ 、Sn 4+ 、Si 4+ 、Nb 5+ One or more of the following;
heating and evaporating the obtained slurry in an oil bath pan to dryness to form xerogel;
and (3) placing the obtained xerogel in a crucible, preprocessing for 3-6 hours at 400-500 ℃, grinding the preprocessed powder, tabletting, placing the obtained powder in the crucible, calcining for 10-24 hours at 700-900 ℃ in air or oxygen atmosphere, rapidly cooling to room temperature within 1-300 seconds, and grinding to obtain the sodium ion battery anode active material.
5. An electrode material for a sodium ion secondary battery, characterized in that the electrode material comprises: a conductive additive, a binder and the sodium ion battery positive electrode active material of the self-replenishing sodium of claim 1.
6. The electrode material for a sodium ion secondary battery according to claim 5, wherein the conductive additive comprises: carbon black, acetylene black, graphite powder, carbon nanotubes, graphene, nitrogen-doped carbon;
the binder comprises one or more of polyvinylidene fluoride PVDF, sodium alginate, sodium carboxymethyl cellulose CMC and styrene butadiene rubber SBR.
7. A positive electrode sheet comprising the electrode material of a sodium ion secondary battery as claimed in claim 5 or 6.
8. A sodium ion secondary battery comprising the positive electrode sheet of claim 7.
CN202110105222.XA 2021-01-26 2021-01-26 Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof Active CN114790013B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110105222.XA CN114790013B (en) 2021-01-26 2021-01-26 Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110105222.XA CN114790013B (en) 2021-01-26 2021-01-26 Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114790013A CN114790013A (en) 2022-07-26
CN114790013B true CN114790013B (en) 2023-10-13

Family

ID=82459634

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110105222.XA Active CN114790013B (en) 2021-01-26 2021-01-26 Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114790013B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115377409A (en) * 2022-08-09 2022-11-22 南开大学 High-performance sodium ion battery layered oxide electrode material
CN115207341B (en) * 2022-08-10 2023-08-22 湘潭大学 Preparation method of high-entropy oxide sodium ion battery positive electrode material
CN115385397A (en) * 2022-09-16 2022-11-25 惠州亿纬锂能股份有限公司 Sodium-supplementing cathode material and preparation method and application thereof
CN115504520A (en) * 2022-09-27 2022-12-23 湖南金富力新能源股份有限公司 Layered sodium-ion battery positive electrode material and preparation method and application thereof
CN115954445B (en) * 2022-10-31 2024-01-02 湖南驼峰新能源有限公司 Nanometer sodium oxalate composite positive electrode active material and application thereof
CN115763947B (en) * 2022-11-07 2023-06-16 南开大学 Anshi sodium ion soft package battery
CN115663173A (en) * 2022-11-10 2023-01-31 赣州立探新能源科技有限公司 Sodium-rich layered oxide material and preparation method and application thereof
CN115611323B (en) * 2022-11-25 2023-03-21 江苏正力新能电池技术有限公司 Positive electrode material, preparation method thereof, positive electrode piece and sodium-ion battery
CN115626669B (en) * 2022-12-20 2023-04-25 江苏正力新能电池技术有限公司 Conversion type material synergistic modified sodium ion battery O3 phase layered oxide cathode material and preparation method and application thereof
CN115924999A (en) * 2023-02-24 2023-04-07 广东金晟新能源股份有限公司 Copper ion doped nickel-iron-manganese-based ternary precursor, preparation method and application thereof
CN115882159B (en) * 2023-03-08 2023-05-12 四川中科兴业高新材料有限公司 Preparation method of sodium battery diaphragm based on PPS
CN116190632B (en) * 2023-05-04 2023-07-18 溧阳中科海钠科技有限责任公司 Composite layered oxide positive electrode material and sodium ion battery
CN117199360B (en) * 2023-08-14 2024-03-26 中南大学 Sodium carbonate/carbon composite positive electrode sodium supplementing additive, preparation method thereof and application thereof in negative electrode-free sodium metal battery
CN117012948A (en) * 2023-09-27 2023-11-07 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof and sodium ion battery
CN117228745B (en) * 2023-11-10 2024-01-23 蜂巢能源科技股份有限公司 Sodium ion battery anode sodium supplementing agent and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104795561A (en) * 2014-07-25 2015-07-22 中国科学院物理研究所 Layered O3-phase nickel oxide-contained positive electrode material and preparation method and application thereof
CN107579213A (en) * 2017-08-14 2018-01-12 北京工业大学 A kind of multiphase sodium ion battery electrode material structure design and performance control technique
CN107706375A (en) * 2017-09-25 2018-02-16 济宁市无界科技有限公司 The method for preparing manganese base sodium ion composite oxide positive pole material
CN109585795A (en) * 2017-09-29 2019-04-05 中国科学院物理研究所 Mixed phase structure layered oxide material and its preparation method and application
CN109786715A (en) * 2019-01-28 2019-05-21 中南大学 A method of copper-based rich sodium layered oxide material is prepared based on chalcopyrite
CN110838576A (en) * 2018-08-17 2020-02-25 中国科学院物理研究所 Doped coated sodium-ion battery positive electrode material and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020098146A1 (en) * 2000-11-27 2002-07-25 National Institute For Materials Science Lamellar sodium-cobalt-manganese oxide and method for manufacturing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104795561A (en) * 2014-07-25 2015-07-22 中国科学院物理研究所 Layered O3-phase nickel oxide-contained positive electrode material and preparation method and application thereof
CN107579213A (en) * 2017-08-14 2018-01-12 北京工业大学 A kind of multiphase sodium ion battery electrode material structure design and performance control technique
CN107706375A (en) * 2017-09-25 2018-02-16 济宁市无界科技有限公司 The method for preparing manganese base sodium ion composite oxide positive pole material
CN109585795A (en) * 2017-09-29 2019-04-05 中国科学院物理研究所 Mixed phase structure layered oxide material and its preparation method and application
CN110838576A (en) * 2018-08-17 2020-02-25 中国科学院物理研究所 Doped coated sodium-ion battery positive electrode material and preparation method and application thereof
CN109786715A (en) * 2019-01-28 2019-05-21 中南大学 A method of copper-based rich sodium layered oxide material is prepared based on chalcopyrite

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Abhinav Tripathi et al..Developing an O3 type layered oxide cathode and its application in 18650 commercial type Na-ion batteries.《Journal of Materials Chemistry A》.2019,第7卷第25944-25960页. *
Developing an O3 type layered oxide cathode and its application in 18650 commercial type Na-ion batteries;Abhinav Tripathi et al.;《Journal of Materials Chemistry A》;第7卷;第25944-25960页 *
新一代储能钠离子电池正极材料的改性研究进展;朱子翼;董鹏;张举峰;黎永泰;肖杰;曾晓苑;李雪;张英杰;;化工进展(第03期);第234-247页 *
锂离子电池正极材料Li1+xV3O8的改性研究进展;曹笃盟等;《材料导报》;第18卷;第263-265页 *

Also Published As

Publication number Publication date
CN114790013A (en) 2022-07-26

Similar Documents

Publication Publication Date Title
CN114790013B (en) Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof
CN113258060B (en) Sodium ion battery high-nickel layered oxide material and preparation method and application thereof
CN107403913B (en) Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof
JP4063350B2 (en) Method for producing composite oxide using sol-gel method
Yuan et al. Surfactant-assisted hydrothermal synthesis of V2O5 coated LiNi1/3Co1/3Mn1/3O2 with ideal electrochemical performance
Yi et al. High-performance xLi2MnO3·(1-x) LiMn1/3Co1/3Ni1/3O2 (0.1⿤ x⿤ 0.5) as Cathode Material for Lithium-ion Battery
KR100946387B1 (en) Olivine type positive active material precursor for lithium battery, olivine type positive active material for lithium battery, method for preparing the same, and lithium battery comprising the same
CN111370697B (en) Lithium manganese iron phosphate/carbon-coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery
WO2015001631A1 (en) Lithium ion secondary battery positive electrode active material, lithium ion secondary battery positive electrode, lithium ion secondary battery, and method for manufacturing said active material, said positive electrode, and said battery
CN114843469B (en) MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof
CN102299316A (en) Layered oxide lithium ion battery anode and preparation method thereof
CN110556531A (en) Anode material, preparation method thereof and lithium ion battery containing anode material
CN115207340A (en) Sodium ion battery layered oxide positive electrode material and preparation method and application thereof
CN112490444A (en) Lithium ion secondary battery positive electrode material and preparation method thereof
CN113845153A (en) Multi-element high-entropy solid solution cathode material and preparation method and application thereof
CN112701276A (en) Quaternary polycrystalline positive electrode material and preparation method and application thereof
CN110085854B (en) Lithium vanadium phosphate cathode material and preparation method thereof
CN113066980B (en) Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material
CN116639740A (en) Cobalt-free lithium-rich manganese-based positive electrode material and preparation method thereof
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
CN107516729B (en) Transition metal layer lithium-containing layered electrode material for symmetrical secondary battery and preparation method and application thereof
CN113113588B (en) Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy
CN114671471A (en) Spinel/layered heterostructure modified cobalt-free lithium-rich manganese-based positive electrode material and preparation method thereof
CN115133018A (en) Preparation method and application of positive electrode lithium supplement additive
KR101406512B1 (en) Positive active material, method of preparing the same, and lithium secondary battery using the same

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
GR01 Patent grant
GR01 Patent grant