CN116259743A - Titanium doped sodium ion battery anode layered oxide material, preparation method and application - Google Patents

Titanium doped sodium ion battery anode layered oxide material, preparation method and application Download PDF

Info

Publication number
CN116259743A
CN116259743A CN202310234276.5A CN202310234276A CN116259743A CN 116259743 A CN116259743 A CN 116259743A CN 202310234276 A CN202310234276 A CN 202310234276A CN 116259743 A CN116259743 A CN 116259743A
Authority
CN
China
Prior art keywords
sodium ion
titanium
ion battery
positive
layered oxide
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
CN202310234276.5A
Other languages
Chinese (zh)
Inventor
容晓晖
张世光
苏韵
胡勇胜
陈立泉
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.)
Yangtze River Delta Physics Research Center Co ltd
Institute of Physics of CAS
Original Assignee
Yangtze River Delta Physics Research Center Co ltd
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 Yangtze River Delta Physics Research Center Co ltd, Institute of Physics of CAS filed Critical Yangtze River Delta Physics Research Center Co ltd
Priority to CN202310234276.5A priority Critical patent/CN116259743A/en
Publication of CN116259743A publication Critical patent/CN116259743A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a titanium doped sodium ion battery anode layered oxide material, a preparation method and application thereof, wherein the chemical general formula of the titanium doped sodium ion battery anode layered oxide material is Na x Ni (1‑y)/2 Mn (1‑y)/2 Ti y O 2 X is more than or equal to 0.7 and less than 1, and y is more than or equal to 0.01 and less than 0.3; titanium ions in the titanium doped sodium ion battery anode layered oxide material are positive tetravalent, manganese ions are positive trivalent and positive tetravalent, and nickel ions are positive divalent; titanium doped sodium ion battery anode layered oxide material for anode activity of sodium ion secondary batteryThe material, when charged in the first week, the nickel ions are changed from positive divalent to positive tetravalent, and the manganese ions of positive trivalent are changed from positive trivalent to positive tetravalent; during the first week of discharge, nickel ions are changed from positive tetravalent to positive divalent again, and the charge and discharge process after the second week only has the valence change of nickel ions, and both manganese ions and titanium ions are unchanged.

Description

Titanium doped sodium ion battery anode layered oxide material, preparation method and application
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a titanium doped sodium ion battery anode layered oxide material, a preparation method and application thereof.
Background
With the continuous development of society, non-renewable fossil fuels such as petroleum and natural gas gradually become a main source of social energy supply, and a series of serious environmental pollution problems are caused by the large-scale exploitation of fossil fuels, so that the dependence of fossil fuels is reduced, and the searching and development of novel renewable energy sources are imperative. The existing renewable energy sources comprise wind energy, tidal energy, solar energy, hydrogen energy and the like, but the novel energy sources are somewhat dependent on the changes of climate, time, geographical position and the like, can not meet the social demands at any time, and have great problems and difficulties in realizing the efficient conversion among various renewable energy sources and are difficult to be utilized efficiently. Electrochemical energy storage dominates in a variety of energy storage device applications. The secondary battery mainly comprises a lead-acid battery, a nickel-cadmium battery, a nickel-hydrogen battery and a lithium battery, and the lead-acid battery is used at the earliest in 1890, and is used in a large scale due to low price, mature technology and high safety, but has a series of problems of low energy density, short service life, environmental protection and the like. Nickel-cadmium cells, although better at high and low temperatures, have a lower energy density that prevents their mass production, appeared in the fifth sixties of the last century. The nickel-hydrogen battery has the advantages of effectively improving the energy density, inhibiting the large-scale application of the nickel-hydrogen battery due to high price, improving the working voltage until the lithium ion battery in nineties of the last century, rapidly occupying the social market due to a series of advantages of low price, rapid charging, energy density, long cycle life and the like, and being widely applied to the fields of various electronic devices, aerospace, traffic and the like at present, but rapidly increasing the price of lithium resources along with the large exploitation and use of the lithium resources. The lithium resources are limited in their content in the crust and are unevenly stored. The consumption of global lithium resources has increased from 13 ten thousand tons in 2011 to 30 ten thousand tons in 2020, and the limited resources and the gradually increasing production cost inhibit the large-scale application of the lithium resources in energy storage equipment, so that the development prospect is difficult.
The sodium element and the lithium element belong to the same main group, have the same physical and chemical properties as lithium, and the sodium ion battery has the same working principle as the lithium ion battery, so that the production technology and the preparation method of the lithium ion battery can be directly used in the large-scale production process, and the industrialization process of the sodium ion battery is quickened. The sodium element is rich in the crust, is uniformly distributed, has low production cost and the like, can be applied to large-scale energy storage equipment, and can be used for alleviating the problem of serious shortage of lithium resources and meeting the requirements of social energy supply by developing a novel sodium ion battery.
The positive electrode material of the sodium ion battery comprises transition metal layered oxides, polyanions, prussian blue and organic matters, at present, sodium ion is only studied in the primary stage, the energy density of the sodium ion battery is half of that of a lithium ion battery, but the energy density of the sodium ion battery is far higher than that of a lead-acid battery. The earliest research is that the layered oxide anode material has a general structural formula of Na x MO 2 (M represents one or more transition metal elements).
The high-performance layered oxide cathode material is important to sodium ion battery industrialization. However, a solid electrolyte interface film (SEI) is formed on the negative electrode side in the full cell, consuming active sodium ions, resulting in irreversible capacity loss, thereby limiting the increase of energy density thereof.
The main modification modes of the layered oxide cathode material at present comprise: the positive electrode pre-sodium treatment and the negative electrode pre-sodium treatment, wherein the positive electrode pre-sodium treatment is to select sacrificial sodium salt as an additive to improve the energy density, and the negative electrode pre-sodium treatment is to form a negative electrode half cell and circulate, so that one side of the negative electrode forms SEI, and then the SEI is matched with the positive electrode again to form a full cell.
However, the types of sacrificial sodium salt additives adopted for positive electrode pre-sodium treatment are limited, and the sodium ion battery has the problems of low first week coulombic efficiency and poor cycle performance due to the low capacity utilization rate of the sacrificial sodium salt and the release of byproducts, so that the application of the sodium ion battery in practice is particularly limited.
Disclosure of Invention
The embodiment of the invention provides a titanium doped sodium ion battery anode layered oxide material, a preparation method and application thereof, wherein the secondary spherical particle titanium doped sodium ion battery anode layered oxide material prepared by a coprecipitation method is actually prepared from NaNi 0.5 Mn 0.5 O 2 Is doped with tetravalent titanium and improves Mn 3+ Content of Ti 4+ The spacing of the sodium layers is enlarged, so that the occurrence of irreversible phase change can be inhibited, and the structural stability of the material is improved; when the titanium doped sodium ion battery anode layered oxide material is applied to a sodium ion secondary battery, positive trivalent manganese ions are converted from positive trivalent to positive tetravalent during first-week charging, oxidation-reduction reaction occurs, consumption of sodium ions during generation of a solid electrolyte interface film (SEI) can be inhibited, specific capacity is further improved, and Mn is added 3+/4+ Substitution of part of Ni as redox agent 3+/2+ The use of nickel can be reduced, while not reducing the capacity/energy density of the overall battery, while saving costs.
The titanium doped sodium ion battery anode layered oxide material is applied to a sodium ion full battery, can obviously improve the working voltage of the sodium ion full battery, and has high capacity retention rate and high energy density.
The preparation method of the titanium doped sodium ion battery anode layered oxide material provided by the embodiment of the invention is a coprecipitation method, and the method can obtain polycrystalline secondary particles with uniformly distributed synthetic elements, wherein gaps are compact among the secondary particles, so that the corrosion of electrolyte is reduced, and the occurrence of surface side reactions is reduced.
In a first aspect, an embodiment of the present invention provides a titanium-doped sodium ion battery anode layered oxide material, where the chemical formula of the titanium-doped sodium ion battery anode layered oxide material is Na x Ni (1-y)/2 Mn (1-y)/2 Ti y O 2 ，0.7≤x＜1，0.01≤y＜0.3；
Titanium ions in the titanium doped sodium ion battery anode layered oxide material are positive tetravalent, manganese ions are positive trivalent and positive tetravalent, and nickel ions are positive divalent;
the titanium doped sodium ion battery anode layered oxide material is used for an anode active material of a sodium ion secondary battery, nickel ions are converted from positive divalent to positive tetravalent when charged in the first week, and manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent; during the first week of discharge, nickel ions are changed from positive tetravalent to positive divalent again, and the charging and discharging process after the second week only has the valence change of nickel ions, and manganese ions and titanium ions are unchanged;
the titanium doped sodium ion battery anode layered oxide material is a secondary spherical particle prepared by a coprecipitation method; the secondary spherical particles are formed by closely stacking atomic-level particles;
the titanium doped sodium ion battery anode layered oxide material is O3 phase, and the space group is R-3m.
Preferably, the titanium doped sodium ion battery anode layered oxide material undergoes a phase transition from an O3 phase to a P3 phase when sodium is removed by 0.2mol during charge and discharge, the P3 phase is maintained until the voltage is increased to 4.0V, the phase transition from the P3 phase to the OP2 phase is reversible when the voltage is greater than 4.0V.
In a second aspect, an embodiment of the present invention provides a method for preparing the titanium doped sodium ion battery anode layered oxide material according to the first aspect, where the preparation method is a coprecipitation method, and includes:
weighing a nickel source material, a manganese source material and a titanium source material according to a required stoichiometric ratio, dissolving the materials in deionized water, and uniformly stirring to form a mixed solution;
taking a mixed solution of complexing agent ammonia water and sodium hydroxide as a precipitant, placing the mixed solution into a reaction kettle, and reacting with the precipitant under the nitrogen atmosphere by a peristaltic pump to generate a precipitate;
washing the precipitate with deionized water for at least three times, and uniformly mixing the precipitate with a sodium source material according to a stoichiometric ratio after drying to obtain a precursor;
placing the precursor in a crucible, placing in a muffle furnace, performing heat treatment in an air atmosphere, and discharging to obtain precursor powder;
and grinding and sieving the precursor powder after heat treatment to obtain the titanium doped sodium ion battery anode layered oxide material.
Preferably, the nickel source material includes: one or more of nickel nitrate, nickel sulfate and nickel hydroxide;
the manganese source material comprises: one or more of manganese nitrate, manganese sulfate and manganese hydroxide;
the titanium source material includes: one or more of titanium nitrate, titanium sulfate and titanium hydroxide;
the sodium source material comprises sodium carbonate and/or sodium hydroxide.
Preferably, the temperature of the circulating water bath of the reaction kettle is 50-80 ℃, and the rotating speed is 500-800 rpm;
the pH value in the reaction kettle is controlled between 9.0 and 11.5;
the feeding speed of the peristaltic pump is 100ml/h-300ml/h.
Preferably, the molar ratio of the ammonia water to the sodium hydroxide in the precipitant is [7:3] - [9:1].
Preferably, the temperature of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 12-24 hours.
In a third aspect, an embodiment of the present invention provides a positive electrode sheet, where the positive electrode sheet includes the titanium doped sodium ion battery positive electrode layered oxide material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a sodium ion battery, where the sodium ion battery includes the positive electrode sheet described in the third aspect.
The embodiment of the invention provides a titanium doped sodium ion battery anode layered oxide material, a preparation method and application thereof, wherein the secondary spherical particle titanium doped sodium ion battery anode layered oxide material prepared by a coprecipitation method is actually prepared from NaNi 0.5 Mn 0.5 O 2 Is doped with tetravalent titanium and improves Mn 3+ Content of Ti 4+ The spacing of the sodium layers is enlarged, so that the occurrence of irreversible phase change can be inhibited, and the structural stability of the material is improved; when the titanium doped sodium ion battery anode layered oxide material is applied to a sodium ion secondary battery, positive trivalent manganese ions are converted from positive trivalent to positive tetravalent during first-week charging, oxidation-reduction reaction occurs, consumption of sodium ions during SEI generation can be restrained, specific capacity is further improved, and Mn is added 3+/4+ Substitution of part of Ni as redox agent 3+/2+ The use of nickel can be reduced, while not reducing the capacity/energy density of the overall battery, while saving costs.
The titanium doped sodium ion battery anode layered oxide material is applied to a sodium ion full battery, can obviously improve the working voltage of the sodium ion full battery, and has high capacity retention rate and high energy density.
The preparation method of the titanium doped sodium ion battery anode layered oxide material provided by the embodiment of the invention is a coprecipitation method, and polycrystalline secondary particles with uniformly distributed synthetic elements can be obtained by the method, and gaps are not formed among the secondary particles in a compact manner, so that the corrosion of electrolyte is reduced, and the occurrence of surface side reactions is further reduced.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
Fig. 1 is a flowchart of a preparation method of a titanium doped sodium ion battery anode layered oxide material according to an embodiment of the present invention.
FIG. 2 is an X-ray diffraction (XRD) contrast plot of NaNMT provided in this example 1 versus NaNM prepared in comparative example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) image of NaNMT provided in example 1 and NaNM prepared in comparative example 1.
Fig. 4 is a Nano-scale tomography (Nano-CT) of NaNMT provided in example 1.
Fig. 5 is an Energy Dispersive Spectroscopy (EDS) plot of NaNMT provided in this example 1.
Fig. 6 is a graph comparing the charge and discharge curves of the NaNMT provided in this example 1 and the NaNM assembled sodium half cell prepared in comparative example 1.
Fig. 7 is a graph showing the cycle capacity of the sodium-ion full battery prepared and assembled from the NaNMT provided in this example 1.
Detailed Description
The invention is described in further detail below with reference to the drawings and to specific examples, but it should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the invention in any way, i.e. not as limiting the scope of the invention.
The embodiment of the invention provides a titanium doped sodium ion battery anode layered oxide material, wherein the chemical general formula of the titanium doped sodium ion battery anode layered oxide material is Na x Ni (1-y)/2 Mn (1-y)/2 Ti y O 2 X is more than or equal to 0.7 and less than 1, and y is more than or equal to 0.01 and less than 0.3; the titanium doped sodium ion battery anode layered oxide material is a secondary spherical particle prepared by a coprecipitation method; the secondary spherical particles consist of atomic-scale particles closely packed.
Titanium ions in the titanium doped sodium ion battery anode layered oxide material are positive tetravalent, manganese ions are positive trivalent and positive tetravalent, and nickel ions are positive divalent.
The titanium doped sodium ion battery anode layered oxide material is used as an anode active material of a sodium ion secondary battery, nickel ions are converted from positive divalent to positive tetravalent when charged at the first week, and manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent; during the first week of discharge, nickel ions are changed from positive tetravalent to positive divalent again, and the charge and discharge process after the second week only has the valence change of nickel ions, and both manganese ions and titanium ions are unchanged.
The titanium doped sodium ion battery anode layered oxide material is O3 phase, and the space group is R-3m.
The titanium doped sodium ion battery anode layered oxide material is subjected to phase transition from an O3 phase to a P3 phase when sodium is removed by 0.2mol in the charging and discharging process, the P3 phase is maintained before the voltage is increased to 4.0V, the P3 phase is subjected to phase transition from the P3 phase to the OP2 phase when the voltage is greater than 4.0V, and the phase transition process is reversible.
The embodiment of the invention provides a preparation method of a titanium doped sodium ion battery anode layered oxide material, which is a coprecipitation method, as shown in fig. 1, and specifically comprises the following steps:
step 110, weighing a nickel source material, a manganese source material and a titanium source material according to a required stoichiometric ratio, dissolving the materials in deionized water, and uniformly stirring to form a mixed solution;
wherein the nickel source material comprises: one or more of nickel nitrate, nickel sulfate and nickel hydroxide; the manganese source material includes: one or more of manganese nitrate, manganese sulfate and manganese hydroxide; the titanium source material includes: one or more of titanium nitrate, titanium sulfate and titanium hydroxide;
the amount of deionized water is also stoichiometrically determined.
Step 120, taking a mixed solution of complexing agent ammonia water and sodium hydroxide as a precipitant, placing the mixed solution into a reaction kettle, and reacting with the precipitant to generate a precipitate by a peristaltic pump under the atmosphere of nitrogen;
wherein the mol ratio of ammonia water to sodium hydroxide in the precipitant is [7:3] - [9:1];
the temperature of the circulating water bath of the reaction kettle is 50-80 ℃ and the rotating speed is 500-800 rpm;
the pH value in the reaction kettle is controlled between 9.0 and 11.5, and the pH value in the reaction kettle is controlled by controlling the speed of the precipitant introduced into the reaction kettle;
the peristaltic pump has a feed rate of 100ml/h to 300ml/h.
Step 130, washing the precipitate with deionized water for at least three times, and uniformly mixing the precipitate with a sodium source material according to a stoichiometric ratio after drying to obtain a precursor;
wherein the sodium source material comprises sodium carbonate and/or sodium hydroxide.
Step 140, placing the precursor into a crucible, placing the crucible into a muffle furnace, performing heat treatment in an air atmosphere, and discharging to obtain precursor powder;
wherein the temperature of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 12-24 hours.
Step 150, grinding and sieving the precursor powder after heat treatment to obtain a titanium doped sodium ion battery anode layered oxide material;
wherein the chemical general formula of the obtained titanium doped sodium ion battery anode layered oxide material is Na x Ni (1-y)/ 2 Mn (1-y)/2 Ti y O 2 ，0.7≤x＜1，0.01≤y＜0.3
The titanium doped sodium ion battery anode layered oxide material prepared by the two preparation methods provided by the embodiment of the invention can be used as an anode active material or sodium supplement additive of other anode active materials, is mixed with a conductive agent and a binder to prepare slurry, and is coated on an anode current collector to prepare an anode sheet, wherein the anode current collector comprises but is not limited to aluminum foil.
The positive electrode plate containing the titanium doped sodium ion battery positive electrode layered oxide material provided by the embodiment of the invention is assembled into a sodium ion battery together with a diaphragm, electrolyte or solid electrolyte and a negative electrode plate.
Wherein the separator includes, but is not limited to, any one of a double-sided alumina separator, a separator containing sodium ion solid electrolyte; the base film of the separator includes, but is not limited to: a polyolefin film, a nonwoven fabric film, a fibrous film, and a polyaramid film.
The negative electrode plate comprises any one of a sodium plate or a negative electrode current collector containing a negative electrode active material; specifically, the negative electrode current collector includes, but is not limited to, copper foil or titanium foil, and the active material layer of the surface of the negative electrode current collector further includes a conductive agent and a binder; the negative electrode active material includes, but is not limited to, any one of a carbon material, a tin-based negative electrode material, a silicon-carbon composite material, a nano-oxide material, a titanate-based negative electrode material; the carbon material comprises any one of graphite, hard carbon, carbon fiber, petroleum coke and mesophase carbon microsphere.
The electrolyte includes a solute and a solvent. Wherein the solute is a conductive salt, including but not limited to: sodium perchlorate (NaClO) 4 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium hexafluorophosphate (NaPF) 6 ) Sodium hexafluoroarsenate (NaAsF) 6 ) Sodium trifluoroacetate (CF) 3 COONa). Solvents include, but are not limited to: ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), vinylene Carbonate (VC), fluoroethylene carbonate (FEC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), γ -Butyrolactone (BL), methyl Propionate (MP), methyl Butyrate (MB), ethyl Acetate (EA), ethyl Propionate (EP), propyl Propionate (PP), ethyl Butyrate (EB), 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (deggme), triethylene glycol dimethyl ether (TRGDME), tetraethylene glycol dimethyl ether (teggme), ethyl Methane Sulfonate (EMS), or dimethyl sulfoxide (DMSO).
In order to better understand the technical scheme provided by the invention, the preparation process and the characteristics of the titanium doped sodium ion battery anode layered oxide material are respectively described in the following specific examples.
Example 1
This example provides a titanium doped sodium ion battery anode layered oxide material Na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 The preparation process and performance test of the test equipment specifically comprise the following steps:
(1) Weighing NiSO according to the required stoichiometric ratio 4 ·6H 2 O (analytically pure), mnSO 4 ·H 2 O (analytically pure) and Ti (SO) 4 ) 2 Dissolving (analytically pure) in deionized water, and uniformly stirring to form a mixed solution with the volume of 2mol/L and 4L.
(2) Complexing agent ammonia (NH) 3 ·H 2 3L of mixed solution of O) and NaOH is taken as a precipitator, placed in a reaction kettle, and 100ml of the mixed solution is taken as a peristaltic pump under nitrogen atmosphereThe feed rate of/h is carried into a reaction kettle to react with a precipitator to generate precipitate, wherein the molar ratio of ammonia water to sodium hydroxide is 8.5:1.5, the pH value in the reaction kettle is controlled to be about 9.0, the temperature of a circulating water bath is 50 ℃, and the rotating speed is 600rpm.
(3) Washing the precipitate with deionized water for 5 times, oven drying, and mixing with Na 2 CO 3 Uniformly mixing (analytically pure) according to stoichiometric ratio to obtain the precursor.
(4) Placing the precursor in a crucible, placing in a muffle furnace, performing heat treatment at 900 ℃ for 15 hours in an air atmosphere, and discharging to obtain precursor powder;
(5) Grinding and sieving the precursor powder after heat treatment to finally obtain the titanium doped sodium ion battery anode layered oxide material with a chemical formula of Na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 (abbreviated as NaNMT).
To better illustrate the effect of the examples of the present invention, comparative examples 1-2 are compared with example 1.
Comparative example 1
Preparation of NaNi in this comparative example 0.5 Mn 0.5 O 2 The material is different from example 1 in that Ti (SO) 4 ) 2 (analytically pure) and the amounts of the materials are in accordance with NaNi 0.5 Mn 0.5 O 2 The stoichiometric weighing of (1) is carried out in the same way as in example 1, and NaNi is finally obtained 0.5 Mn 0.5 O 2 Material (abbreviated NaNM).
Performance comparisons are made below with the NaNMT of example 1 versus the NaNM of comparative example 1.
As shown in fig. 2, the XRD comparison patterns of the NaNMT of this example 1 and the NaNM of comparative example 1 show that both materials have pure-phase O3 structure, and have strong crystallinity and no impurity peak.
As shown in FIG. 3, the NaNMT of example 1 and NaNM of comparative example 1 are both secondary particles composed of tightly packed primary particles, and the spherical shape of the particles is largely preserved, and the average diameter of the spherical secondary particles is about 8 μm to 10. Mu.m.
The Nano-scale tomography (Nano-CT) image of the NaNMT of this example 1, as shown in fig. 4, further shows that the NaNMT is a secondary particle composed of a close packing of primary particles.
The Energy Dispersive Spectroscopy (EDS) plot of NaNMT of example 1, as shown in FIG. 5, shows that the basic map indicates that the transition elements Ni, mn and Ti are uniformly distributed over Na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 In the sample.
Positive electrode sheets were prepared and sodium half cells and full cells were assembled using the NaNMT of example 1 and the NaNM of comparative example 1, respectively, and charge and discharge tests were performed on half cells and hard carbon matched full cells, and cycle capacity tests were performed on full cells, with the following specific cell preparation procedure:
preparing a positive electrode plate: naNMT of example 1 and NaNM of comparative example 1 were mixed with acetylene black and polyvinylidene fluoride (PVDF) as binder in a mass ratio of 80:10:10, added with an appropriate amount of N-methylpyrrolidone (NMP) solution, ground in an environment dried at normal temperature to form a slurry, then the slurry was uniformly coated on a current collector aluminum foil to prepare two positive electrode sheets, and after drying under an infrared lamp, cut into (8×8) mm 2 Is a pole piece; the pole piece is dried for 10 hours at 110 ℃ under the vacuum condition, and then is transferred to a glove box for standby.
Assembling a sodium ion half cell: the assembly of the simulated battery was performed in a glove box with Ar atmosphere, using the two positive electrode sheets described above, with sodium metal as the counter electrode, and 1M (molar mass) NaClO, respectively 4 Ethylene carbonate, dimethyl carbonate and propylene carbonate (EC: DMC: PC volume ratio of 1:1:1) +2% fluoroethylene carbonate (FEC) solution are used as electrolyte to assemble two CR2032 button half-cells.
Charge and discharge test procedure for half cell: the charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode, with a discharge cutoff voltage of 2.0V and a charge cutoff voltage of 4.0V.
Comparison of charge and discharge curves of NaNMT of example 1 and NaNM assembled sodium ion cell of comparative example 1, as shown in FIG. 6, it can be seen from the curve comparison of example 1The initial capacity of NaNMT assembled battery of example 1 is lower (NaNi 0.5 Mn 0.5 O 2 Is 143.3mAh/g, na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 Is 139.9 mAh/g) due to the inactive Ti 4+ Substituted for Ni with oxidation-reduction activity 2+ So that the initial capacity is caused to be relatively low; the NaNM material comprises a plurality of voltage platforms and steps, and reflects a complex phase change process; by co-replacing Ni and Mn NaNMT materials with Ti, the charge-discharge curve becomes smooth, mainly consisting of a long plateau of about 2.8V and an inclined portion of 3.0V or more, compared to NaNM, which is due to a wider interlayer distance, corresponding to the phase transition of O3-P3; the inclined part of the charge-discharge curve below 2.5V corresponds to Mn 3+/4+ Is a redox reaction of (a).
Assembling a sodium ion full battery: the assembly of the full cell was performed in an argon glove box using the two positive electrode sheets, each of which was made of hard carbon as a counter electrode and 1M (molar mass) of NaClO 4 Ethylene carbonate, dimethyl carbonate and propylene carbonate (EC: DMC: PC volume ratio of 1:1:1) +2% fluoroethylene carbonate (FEC) solution are used as electrolyte to assemble two CR2032 button type full batteries.
The testing method of the full battery comprises the following steps: using a constant current charge and discharge mode, charge and discharge tests were performed at a C/2 current density, under conditions of a discharge cut-off voltage of 0.5V and a charge cut-off voltage of 4.0V, and coulombic efficiency and cycle capacity graphs of the tests were tested, as shown in fig. 7, it was seen that the cycle capacity retention rate was 83% for 300 cycles, and the cycle was stable. When the full battery is subjected to charge-discharge cycle test under the conditions of 0.5C current density, discharge cut-off voltage of 0.5V and charge cut-off voltage of 4.0V, the initial cycle discharge specific capacity of the full battery in the embodiment 1 can reach 111.4mAh/g, and initial cycle coulomb efficiency is about 82%.
The initial cycle discharge specific capacity and initial cycle coulombic efficiency of the sodium ion half-cells assembled in example 1 and comparative example 1, the initial cycle coulombic efficiency of the full cell at 0.5C current density, the cycle capacity retention at 250 cycles and 300 cycles, and the test data are detailed in table 1.
Comparative example 2
The comparative example adopts a high temperature solid phase method to prepare Na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 The material is prepared by the following steps: weighing Na according to stoichiometric ratio 2 CO 3 、Mn 2 O 3 、NiO、TiO 2 Ball milling for 8 hours, pressing into a circular sheet with the diameter of 14mm under the pressure of 10MPa, calcining for 15 hours at 900 ℃ to obtain Na 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 A material.
Na prepared by the high temperature solid phase method of comparative example 2 0.86 Ni 0.4 Mn 0.4 Ti 0.2 O 2 The material is prepared by adopting the same method as in the embodiment 1, assembling a sodium ion half cell and a full cell, and carrying out charge-discharge and circulation capacity test, wherein the test method is the same as in the embodiment 1, the first-week discharge specific capacity of the sodium ion half cell is 135.7mAh/g, and the first-week coulomb efficiency is about 92.7% and is inferior to that of the NaNMT material prepared by adopting the precipitation method in the embodiment 1, because the NaNMT material prepared by adopting the precipitation method in the embodiment 1 obtains polycrystalline secondary particles with uniformly distributed synthetic elements, the secondary particles are compact and have no gaps, the erosion of electrolyte is reduced, and the occurrence of surface side reactions is reduced.
Comparative example 2 the initial cycle discharge specific capacity and initial cycle coulombic efficiency of the assembled sodium ion half cell, initial cycle Zhou Kulun efficiency, cycle 250 and cycle 300 cycle capacity retention of the full cell at 0.5C current density, were as detailed in table 1.
Example 2
This example provides a titanium doped sodium ion battery anode layered oxide material Na 0.7 Ni 0.475 Mn 0.475 Ti 0.05 O 2 The preparation process and performance test of the test equipment specifically comprise the following steps:
(1) Ni (NO) is weighed according to the stoichiometric ratio 3 ) 2 (analytical grade), mn (OH) 2 (analytically pure) and Ti (NO) 3 ) 4 Dissolving (analytically pure) in deionized water, stirring uniformly to form a mixed solution of 2mol/L,the volume of the mixed solution was 6L.
(2) Complexing agent ammonia (NH) 3 ·H 2 And O) and NaOH 5L are taken as precipitants, the mixed solution is placed in a reaction kettle, and is brought into the reaction kettle to react with the precipitants at a feeding speed of 300ml/h through a peristaltic pump under the atmosphere of nitrogen, so as to generate precipitates, wherein the molar ratio of ammonia water to sodium hydroxide is 9:1, the pH value in the reaction kettle is controlled to be about 11.0, the temperature of a circulating water bath is 60 ℃, and the rotating speed is 700rpm.
(3) Washing the precipitate with deionized water for 5 times, oven drying, and mixing with Na 2 CO 3 Uniformly mixing (analytically pure) according to stoichiometric ratio to obtain the precursor.
(4) Placing the precursor in a crucible, placing in a muffle furnace, performing heat treatment at 800 ℃ for 24 hours in an air atmosphere, and discharging to obtain precursor powder;
(5) Grinding and sieving the precursor powder after heat treatment to finally obtain the titanium doped sodium ion battery anode layered oxide material with a chemical formula of Na 0.7 Ni 0.475 Mn 0.475 Ti 0.05 O 2 。
Using Na prepared in example 2 0.7 Ni 0.475 Mn 0.475 Ti 0.05 O 2 The sodium half cell and full cell were assembled and tested, and the assembly and testing procedure was the same as in example 1.
Example 2 the initial cycle discharge specific capacity and initial cycle coulombic efficiency of assembled sodium ion half-cells, initial cycle coulombic efficiency of full cells at 0.5C current density, cycling capacity retention for 250 cycles and 300 cycles, test data are detailed in table 1.
Example 3
This example provides a titanium doped sodium ion battery anode layered oxide material Na 0.9 Ni 0.35 Mn 0.35 Ti 0.3 O 2 The preparation process and performance test of the test equipment specifically comprise the following steps:
(1) Ni (OH) is weighed according to the stoichiometric ratio 2 (analytical grade), mn (OH) 2 (analytically pure) and Ti (OH) 4 Dissolving in deionized water, stirringUniformly stirring to form a mixed solution with the volume of 2mol/L and the volume of the mixed solution is 6L.
Wherein the nickel source material comprises: one or more of nickel nitrate, nickel sulfate and nickel hydroxide; the manganese source material includes: one or more of manganese nitrate, manganese sulfate and manganese hydroxide; the titanium source material includes: one or more of titanium nitrate, titanium sulfate and titanium hydroxide;
the amount of deionized water is also stoichiometrically determined.
(2) Complexing agent ammonia (NH) 3 ·H 2 And O) and NaOH 5L are taken as precipitants, the mixed solution is placed in a reaction kettle, and is brought into the reaction kettle to react with the precipitants at a feeding speed of 200ml/h through a peristaltic pump under the atmosphere of nitrogen, so as to generate precipitates, wherein the molar ratio of ammonia water to sodium hydroxide is 7:3, the pH value in the reaction kettle is controlled to be about 10.0, the temperature of a circulating water bath is 80 ℃, and the rotating speed is 800rpm.
(3) The precipitate was washed 3 times with deionized water, dried and then uniformly mixed with NaOH (analytically pure) according to the stoichiometric ratio to obtain the precursor.
(4) Placing the precursor in a crucible, placing in a muffle furnace, performing heat treatment at 1000 ℃ for 20 hours in an air atmosphere, and discharging to obtain precursor powder;
(5) Grinding and sieving the precursor powder after heat treatment to finally obtain the titanium doped sodium ion battery anode layered oxide material with a chemical formula of Na 0.9 Ni 0.35 Mn 0.35 Ti 0.3 O 2 。
Using Na prepared in example 3 0.9 Ni 0.35 Mn 0.35 Ti 0.3 O 2 The sodium half cell and full cell were assembled and tested, and the assembly and testing procedure was the same as in example 1.
Example 3 initial cycle discharge specific capacity and initial cycle coulombic efficiency of assembled sodium ion half-cells, initial cycle coulombic efficiency of full cells at 0.5C current density, cycle capacity retention at 250 cycles and 300 cycles, test data are detailed in table 1.
Table 1 is a summary of the initial cycle coulombic efficiency and specific discharge capacity values of the assembled sodium ion half-cells of examples 1-3 and comparative examples 1-2, and the cycle capacity retention test data for the initial cycle coulombic efficiency, 250 cycles, and 300 cycles of the sodium ion full-cells.
Figure BDA0004121495820000141
Figure BDA0004121495820000151
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 (9)

1. A titanium doped sodium ion battery anode layered oxide material is characterized in that the chemical general formula of the titanium doped sodium ion battery anode layered oxide material is Na x Ni (1-y)/2 Mn (1-y)/2 Ti y O 2 ，0.7≤x＜1，0.01≤y＜0.3；
Titanium ions in the titanium doped sodium ion battery anode layered oxide material are positive tetravalent, manganese ions are positive trivalent and positive tetravalent, and nickel ions are positive divalent;
the titanium doped sodium ion battery anode layered oxide material is used for an anode active material of a sodium ion secondary battery, nickel ions are converted from positive divalent to positive tetravalent when charged in the first week, and manganese ions of positive trivalent are converted from positive trivalent to positive tetravalent; during the first week of discharge, nickel ions are changed from positive tetravalent to positive divalent again, and the charging and discharging process after the second week only has the valence change of nickel ions, and manganese ions and titanium ions are unchanged;
the titanium doped sodium ion battery anode layered oxide material is a secondary spherical particle prepared by a coprecipitation method; the secondary spherical particles are formed by closely stacking atomic-level particles;
the titanium doped sodium ion battery anode layered oxide material is O3 phase, and the space group is R-3m.
2. The titanium-doped sodium ion battery positive electrode layered oxide material according to claim 1, wherein the titanium-doped sodium ion battery positive electrode layered oxide material undergoes a phase transition from an O3 phase to a P3 phase when sodium is removed by 0.2mol during charge and discharge, maintains the P3 phase before boosting to 4.0V, is phase-transitioned from the P3 phase to an OP2 phase at a voltage of more than 4.0V, and the phase transition is reversible.
3. A method for preparing the titanium-doped sodium ion battery anode layered oxide material according to any one of claims 1-2, wherein the preparation method is a coprecipitation method, comprising:
weighing a nickel source material, a manganese source material and a titanium source material according to a required stoichiometric ratio, dissolving the materials in deionized water, and uniformly stirring to form a mixed solution;
taking a mixed solution of complexing agent ammonia water and sodium hydroxide as a precipitant, placing the mixed solution into a reaction kettle, and reacting with the precipitant under the nitrogen atmosphere by a peristaltic pump to generate a precipitate;
washing the precipitate with deionized water for at least three times, and uniformly mixing the precipitate with a sodium source material according to a stoichiometric ratio after drying to obtain a precursor;
placing the precursor in a crucible, placing in a muffle furnace, performing heat treatment in an air atmosphere, and discharging to obtain precursor powder;
and grinding and sieving the precursor powder after heat treatment to obtain the titanium doped sodium ion battery anode layered oxide material.
4. A method of preparing as claimed in claim 3, wherein the nickel source material comprises: one or more of nickel nitrate, nickel sulfate and nickel hydroxide;
the manganese source material comprises: one or more of manganese nitrate, manganese sulfate and manganese hydroxide;
the titanium source material includes: one or more of titanium nitrate, titanium sulfate and titanium hydroxide;
the sodium source material comprises sodium carbonate and/or sodium hydroxide.
5. The method according to claim 3, wherein the temperature of the circulating water bath of the reaction vessel is 50-80 ℃ and the rotation speed is 500-800 rpm;
the pH value in the reaction kettle is controlled between 9.0 and 11.5;
the feeding speed of the peristaltic pump is 100ml/h-300ml/h.
6. The method according to claim 3, wherein the molar ratio of ammonia water to sodium hydroxide in the precipitant is from [7:3] to [9:1].
7. A method of preparation according to claim 3 wherein the heat treatment is carried out at a temperature between 600 ℃ and 1000 ℃ for a period of time between 12 hours and 24 hours.
8. A positive electrode sheet, characterized in that the positive electrode sheet comprises the titanium doped sodium ion battery positive electrode layered oxide material according to any one of the preceding claims 1-2.
9. A sodium ion battery comprising the positive electrode sheet of claim 8.
CN202310234276.5A 2023-03-10 2023-03-10 Titanium doped sodium ion battery anode layered oxide material, preparation method and application Pending CN116259743A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310234276.5A CN116259743A (en) 2023-03-10 2023-03-10 Titanium doped sodium ion battery anode layered oxide material, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310234276.5A CN116259743A (en) 2023-03-10 2023-03-10 Titanium doped sodium ion battery anode layered oxide material, preparation method and application

Publications (1)

Publication Number Publication Date
CN116259743A true CN116259743A (en) 2023-06-13

Family

ID=86679151

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310234276.5A Pending CN116259743A (en) 2023-03-10 2023-03-10 Titanium doped sodium ion battery anode layered oxide material, preparation method and application

Country Status (1)

Country Link
CN (1) CN116259743A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117117197A (en) * 2023-10-23 2023-11-24 内蒙古大学 Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117117197A (en) * 2023-10-23 2023-11-24 内蒙古大学 Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof
CN117117197B (en) * 2023-10-23 2024-01-16 内蒙古大学 Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN109980219B (en) Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof
CN107369825B (en) Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof
US20220216471A1 (en) Lithium supplementing material and positive electrode containing same
CN103435105B (en) A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application
CN103904321B (en) The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4
WO2021042983A1 (en) Positive electrode active material and preparation method therefor, positive electrode plate, lithium-ion secondary battery and battery module comprising same, battery pack, and device
CN105118987A (en) Preparation method of high-capacity lithium-rich anode material
CN114628677B (en) Copper-doped potassium manganate electrode material, preparation method thereof and application thereof in potassium ion battery
CN113675394B (en) Potassium ion battery positive electrode material, preparation method and potassium ion battery
CN113903884B (en) Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN115611773B (en) Lithium supplementing compound, preparation method thereof and lithium ion battery
CN114937764A (en) Cobalt disulfide composite material protected by double carbon layers and preparation method and application thereof
CN114497533A (en) In-situ spinel modified low-cobalt spherical lithium-rich manganese-based positive electrode material and preparation method thereof
CN116259743A (en) Titanium doped sodium ion battery anode layered oxide material, preparation method and application
Jiang et al. Influence of co-precipitation temperature on microstructure and electrochemical properties of Li [Li 0.2 Mn 0.54 Ni 0.13 Co 0.13] O 2 cathode materials for lithium ion batteries
CN116190633B (en) Layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application
CN115954482A (en) Layered oxide composite material, preparation method thereof, positive plate and sodium ion battery
CN115872462A (en) Preparation method of high-entropy oxide positive electrode material of potassium ion battery
CN115340134A (en) Preparation method of nickel cobalt lithium manganate precursor with coating structure and lithium ion battery containing precursor
CN112751014A (en) Aqueous energy storage battery based on layered vanadium oxide negative electrode
CN113422027A (en) Positive electrode composite material and preparation method and application thereof
Li et al. Nano-grinding derived high-performance Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 cathode material: from kilogram-scale synthesis to its pouch cell
CN110600732A (en) Preparation method of polyanion negative electrode material cobalt pyrophosphate
CN114538459B (en) Preparation method of borate lithium ion battery anode material and lithium ion 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
CB02 Change of applicant information

Address after: 213300 Room 403, No. 87 Shangshang Road, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province (Zhongguancun Science and Technology Industrial Park, Jiangsu Province)

Applicant after: Yangtze River Delta Physics Research Center Co.,Ltd.

Applicant after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES

Address before: No. 1, Zhongguancun Avenue, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province, 213300

Applicant before: Yangtze River Delta Physics Research Center Co.,Ltd.

Applicant before: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES

CB02 Change of applicant information