WO2025002026A1 - Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion - Google Patents

Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion Download PDF

Info

Publication number
WO2025002026A1
WO2025002026A1 PCT/CN2024/100849 CN2024100849W WO2025002026A1 WO 2025002026 A1 WO2025002026 A1 WO 2025002026A1 CN 2024100849 W CN2024100849 W CN 2024100849W WO 2025002026 A1 WO2025002026 A1 WO 2025002026A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
ion battery
sodium ion
electrode material
containing compound
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.)
Ceased
Application number
PCT/CN2024/100849
Other languages
English (en)
Chinese (zh)
Inventor
刘何丽
李顺利
卢林
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.)
Trina Storage Solutions (Jiangsu) Co Ltd
Original Assignee
Trina Storage Solutions (Jiangsu) Co Ltd
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 Trina Storage Solutions (Jiangsu) Co Ltd filed Critical Trina Storage Solutions (Jiangsu) Co Ltd
Publication of WO2025002026A1 publication Critical patent/WO2025002026A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/50—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention belongs to the technical field of battery materials, and in particular relates to a sodium ion battery positive electrode material and a preparation method, a positive electrode and a sodium ion battery.
  • the layered oxides in the positive electrode materials of sodium-ion batteries have the same synthesis process as the layered oxide positive electrodes such as lithium cobalt oxide and ternary materials widely used in lithium-ion batteries, so they are expected to become the fastest large-scale industrialized positive electrode materials.
  • the surface of the O3 layered oxide positive electrode material of sodium-ion batteries has a high level of residual alkali, which will cause gas production during the cycle and react with the electrolyte to deteriorate the cycle.
  • more residual alkali will also cause process problems such as gelation of the slurry during the slurrying process. Therefore, it is necessary to reduce the residual alkali to improve the interface stability of the positive electrode material.
  • the present invention provides a sodium ion battery positive electrode material and a preparation method thereof.
  • the technical solution of the present invention includes:
  • a sodium ion battery positive electrode material comprises a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the positive electrode substrate is doped with an M element, wherein the M element is one or more of Al, Mg, Ti, Zr, Y, La, Cu, Zn, Ca, Li or B elements.
  • the present invention reduces the amount of residual alkali on the surface of the positive electrode material through the coating layer and the doped effective elements, fully improves the air stability of the positive electrode material of the O3 type sodium ion battery, effectively reduces the gas production, reduces the side reaction with the electrolyte, and improves the cycle performance of the material.
  • the coated tungsten-containing compound and the doped effective element can not only reduce the irreversible phase change of the material during the cycle process and improve the structural stability of the material, but also react with the residual alkali on the surface of the positive electrode, such as NaOH, Na2CO3 , etc.
  • the thickness of the positive electrode substrate is 3 to 10 mm, and the thickness of the wrapping layer is 2 to 10 nm.
  • a method for preparing a positive electrode material for a sodium ion battery, used for preparing the positive electrode material for the sodium ion battery comprises the following steps:
  • NixFeyMnzMn (OH) 2 Mixing NixFeyMnzMn (OH) 2 and a sodium - containing compound , wherein the molar ratio of metal cations to Na ions in NixFeyMnzMn (OH) 2 is 1:(1-2), and after fully mixing, sintering the mixture in two stages in an air flow to obtain NamNixFeyMnzMnO2 material ;
  • the present invention can not only improve the structural stability of the material and reduce the irreversible phase change of the material during the cycle by coating the tungsten-containing compound and the doped effective element.
  • the residual alkali such as NaOH and Na 2 CO 3 reacts to convert it into low alkalinity such as sodium tungstate, making it a material with high ion conductivity, improving the air stability and processability of the positive electrode material.
  • the reduction of surface residual alkali can effectively reduce the gas generation of the positive electrode material during the cycle and improve the cycle stability.
  • step S1 NixFeyMnzMn (OH) 2 and sodium carbonate are mixed , wherein the molar ratio of metal cations to Na ions in NixFeyMnzMn (OH) 2 is 1:( 1-1.4 ), and after being fully mixed, the mixture is sintered in two stages in an air flow or an oxygen flow to obtain NamNixFeyMnzMnO2 material .
  • the method for preparing Ni x Fe y Mn z Mn (OH) 2 in step S1 comprises the following steps:
  • S1-1 Mixing a nickel-containing compound, an iron-containing compound and a manganese-containing compound with a M-containing compound in a molar ratio of Ni:Fe:Mn:M of x:y:z:n, neutralizing the solution after mixing evenly, and obtaining a ternary hydroxide precursor precipitate by a coprecipitation method;
  • the M element in the M-containing compound is one or more of Al, Mg, Ti, Zr, Y, La, Cu, Zn, Ca, Li or B elements.
  • the M-containing compound is one of an aluminum sulfate solution, a titanium sulfate solution, and a magnesium sulfate solution.
  • step S1-1 a nickel sulfate compound, an iron sulfate solution and a manganese sulfate and an M-containing compound are mixed according to a molar ratio of Ni:Fe:Mn:M of x:y:z:n. After mixing evenly, ammonia water and a NaOH solution are added to the solution for neutralization, and a ternary hydroxide precursor precipitate is obtained by a coprecipitation method.
  • the tungsten-containing compound is one or more of ammonium metatungstate, ammonium paratungstate, tungsten oxide and tungstic acid.
  • the two-stage sintering process in step S1 is The process comprises the following steps:
  • Another aspect of the present invention further provides a positive electrode of a sodium ion battery, which uses the aforementioned positive electrode material for a sodium ion battery.
  • a sodium ion battery comprising the positive electrode as described above.
  • the present invention reduces the residual alkali on the surface of the positive electrode material by coating the tungsten-containing compound and the doped effective elements, fully improves the air stability of the positive electrode material of the O3 type sodium ion battery, effectively reduces the gas production, reduces the side reaction with the electrolyte, and improves the cycle performance of the material.
  • the encapsulated tungsten-containing compound and the doped effective element can not only reduce the irreversible phase change of the material during the cycle and improve the structural stability of the material, but also react with the residual alkali on the surface of the positive electrode, such as NaOH, Na2CO3 , etc. , to convert into low-alkalinity materials such as sodium tungstate with high ion conductivity, thereby improving the air stability and processability of the positive electrode material.
  • the reduction of the residual alkali on the surface can effectively reduce the gas production of the positive electrode material during the cycle and improve the cycle stability.
  • the coating layer and the doped effective element body in the present invention can play a synergistic role.
  • the doped elements can effectively inhibit the irreversible phase change during the sodium removal process, and the coated tungsten-containing compound can react with the residual alkali on the surface to generate low-alkalinity fast ion conductors such as sodium tungstate, thereby avoiding gas production caused by strong alkalinity, and also avoiding the instability and processing problems of the slurry caused by strong alkalinity.
  • the tungsten-containing compound coated on the particle surface can prevent the continuation of the side reaction between the particle surface and the electrolyte, thereby improving the stability of the material during the cycle.
  • FIG. 1 is a comparison chart of the slurry stability of Example 1 and Comparative Example 1.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with an Al element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 .
  • this embodiment also provides a method for preparing the sodium ion battery positive electrode material coated with tungsten compound and co-modified with Al element doping, comprising the following steps:
  • the obtained hydroxide precursor Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 (OH) 2 and sodium carbonate were mixed according to the molar ratio of metal cations in the hydroxide precursor to Na ions of 1:1.03. After being fully mixed, the mixture was sintered in two stages in an air flow:
  • This embodiment provides a sodium ion battery positive electrode material coated with a tungsten compound and co-modified with a Mg element doping, comprising a positive electrode substrate and a coating layer, wherein the coating layer is coated on the surface of the positive electrode substrate.
  • the tungsten-containing compound on the surface, the chemical formula of the positive electrode substrate is NaNi 0.4 Fe 0.2 Mn 0.35 Mg 0.05 (OH) 2 .
  • the method for preparing the sodium ion battery positive electrode material coated with a tungsten compound and co-modified with a Mg element doping comprises the following steps:
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with a Mg element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Mg 0.05 (OH) 2 .
  • the method for preparing the sodium ion battery positive electrode material coated with a tungsten compound and co-modified with a Mg element doping comprises the following steps:
  • Example 2 The remaining steps are similar to those in Example 1 to obtain a battery positive electrode material coated with a tungsten compound and co-modified with a Ti element doping.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with an Al element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • Step S1 is the same as in Example 1;
  • Step S2 After ball-milling and mixing Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 and tungsten trioxide in a mass ratio of 1:0.03, the mixture was calcined at 550° C. for 8 h to obtain a battery positive electrode material coated with tungsten compound and co-modified with Al element doping.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with an Al element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • Step S1 is the same as in Example 1;
  • Step S2 Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 and ammonium paratungstate are mixed in a mass ratio of 1:0.03, and calcined at 550° C. for 9 h to obtain a battery positive electrode material coated with a tungsten compound and co-modified with an Al element.
  • This embodiment provides a sodium ion battery coated with a tungsten compound and co-modified with a Mg element.
  • the positive electrode material of a battery comprises a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • Step S1 is the same as in Example 2;
  • Step S2 The obtained NaNi 0.4 Fe 0.2 Mn 0.35 Mg 0.05 O 2 and ammonium paratungstate are mixed in a mass ratio of 1:0.03, ball-milled, and then calcined at 450° C. for 8 h to obtain a sodium ion battery positive electrode material coated with a tungsten compound and co-modified with a Mg element.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with a Ti element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • Step S1 is the same as in Example 3;
  • Step S2 Mix the obtained Ni 0.4 Fe 0.2 Mn 0.35 Ti 0.05 (OH) 2 and tungstic acid in a mass ratio of 1:0.04, and calcine at 500°C for 10 hours to obtain a battery positive electrode material coated with tungsten compound and co-modified with Ti element doping.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with an Al element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.97 Ni 0.32 Fe 0.32 Mn 0.32 Al 0.04 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • S1 S1-1: Nickel sulfate solution, iron sulfate solution, manganese sulfate and aluminum sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn:Al of 32:32:32:4, and then 2 mol/L ammonia and NaOH solution were added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.32 Fe 0.32 Mn 0.32 Al 0.04 (OH) 2 was produced by coprecipitation. The obtained precipitate was then filtered and washed, and then Dry at 200°C for 4 hours to obtain a dried product.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with a Mg element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.97 Ni 0.32 Fe 0.32 Mn 0.32 Mg 0.04 O 22 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • S1 S1-1: Nickel sulfate solution, iron sulfate solution, manganese sulfate and aluminum sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn:Mg of 32:32:32:4, and then 2 mol of ammonia water and NaOH solution were added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.32 Fe 0.32 Mn 0.32 Mg 0.04 (OH) 2 was produced by coprecipitation. The obtained precipitate was then filtered, washed, and dried at 200°C for 4 hours to obtain a dried product 1.
  • This embodiment provides a sodium ion battery positive electrode material co-modified by coating with a tungsten-containing compound and doping with a Ti element, comprising a positive electrode substrate and a coating layer, wherein the coating layer is a tungsten-containing compound coated on the surface of the positive electrode substrate, and the chemical formula of the positive electrode substrate is Na 0.97 Ni 0.32 Fe 0.32 Mn 0.32 Ti 0.04 O 2 .
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • S1 S1-1: Nickel sulfate solution, iron sulfate solution, manganese sulfate and titanium sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn:Ti of 32:32:32:4, and then 2 mol/L ammonia and NaOH solution were added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.32 Fe 0.32 Mn 0.32 Ti 0.04 (OH) 2 was produced by coprecipitation. The obtained precipitate was then filtered, washed, and dried at 200°C for 4 hours to obtain dried product 10.
  • This embodiment provides a positive electrode of a sodium ion battery, using any of the sodium ion battery positive electrode materials of embodiments 1-10.
  • This embodiment provides a sodium ion battery, which includes the positive electrode described in Example 11.
  • the method for preparing the positive electrode material of a sodium ion battery comprises the following steps:
  • Nickel sulfate solution, iron sulfate solution, manganese sulfate and aluminum sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn:Al of 40:20:35:5, and then 2 mL/L ammonia water and NaOH solution were added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 (OH) 2 was generated by coprecipitation. The obtained precipitate was filtered, washed, and dried at 200°C for 4 hours to obtain a dried product 1.
  • the hydroxide precursor Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 (OH) 2 obtained in step (1) and sodium carbonate are mixed according to a molar ratio of metal cations to Na ions in the hydroxide precursor of 1:1.03. After being fully mixed, the mixture is sintered in two stages in an air flow or an oxygen flow: first, sintered in an air flow at 450° C. for 8 hours, then the sintering temperature is increased to 900° C., and then sintered in an oxygen flow for 10 hours. After sintering, the mixture is cooled in the furnace to obtain Na 0.99 Ni 0.4 Fe 0.2 Mn 0.35 Al 0.05 O 2 material.
  • Nickel sulfate solution, iron sulfate solution, manganese sulfate solution and magnesium sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn:Mg of 40:20:35:5, and then 2 mol/L ammonia water and NaOH solution were added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.4 Fe 0.2 Mn 0.35 Mg 0.05 (OH) 2 was produced by coprecipitation. The obtained precipitate was then filtered, washed, and dried at 200°C for 4 hours to obtain a dried product II.
  • Nickel sulfate solution, iron sulfate solution and manganese sulfate solution were mixed evenly according to the molar ratio of Ni:Fe:Mn of 40:20:40, and then NaOH solution was added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 was produced by coprecipitation. The obtained precipitate was filtered, washed, and dried at 200°C for 4 hours to obtain a dried product.
  • step (1) The hydroxide precursor Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 obtained in step (1) and sodium carbonate are mixed according to the molar ratio of metal cations to Na ions in the hydroxide precursor of 1:1.03. After being fully mixed, the mixture is sintered in an oxygen flow in two stages: first, sintered in an air flow at 450° C. for 8 hours, then the sintering temperature is increased to 900° C., and then sintered in an oxygen flow for 10 hours. After sintering, the mixture is cooled in the furnace to obtain Na 0.99 Ni 0.4 Fe 0.2 Mn 0.4 O 2 material.
  • Nickel sulfate solution, iron sulfate solution and manganese sulfate were mixed evenly according to the molar ratio of Ni:Fe:Mn of 40:20:40, and then 2 mol/L NaOH solution was added to the solution for neutralization, and a ternary hydroxide precursor precipitate Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 was produced by coprecipitation.
  • the obtained precipitate was filtered, washed, and dried at 200°C for 4 hours to obtain a dried product 1;
  • the hydroxide precursor Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 obtained in step (1) and sodium carbonate are mixed in a molar ratio of metal cations to Na ions in the hydroxide precursor of 1:1.03. After being fully mixed, the mixture is sintered in an oxygen flow in two stages: first, sintered in an air flow at 450° C. for 8 hours, then the sintering temperature is increased to 900° C., and then sintered in an oxygen flow for 10 hours. After sintering, the furnace is cooled to obtain Na 0.99 Ni 0.4 Fe 0.2 Mn 0.4 O 2 material.
  • Steps (1) and (2) are the same as those in Comparative Example 1.
  • the prepared positive electrode slurry is evenly coated on an aluminum foil using a scraper, placed in a forced air drying oven, and dried at 120° C. for 20 min. Finally, the dried electrode sheet is rolled and cut to form a positive electrode sheet.
  • Slurry stability test The positive electrode slurry obtained by the above method was tested for slurry viscosity every 0.5h, 1h, 2h, 4h, 8h, 12h, 24h and 48h to obtain the stability of the slurry in the air.
  • pH test of positive electrode material 10 g of positive electrode powder was soaked in 90 mL of deionized water and magnetically stirred for 5 min, and the pH of the leaching solution was tested.
  • Cycle performance test The 1Ah soft-pack battery cell prepared by the above method was charged and discharged at a rate of 1C within a voltage range of 1.5-3.95V. When charged to 3.95V, constant voltage charging was performed with a cut-off current of 0.05C to test the cycle capacity retention rate.
  • FIG1 shows the slurry stability of Example 1 and Comparative Example 1.
  • the sample coated with W compound and doped with elements in Example 1 has better slurry stability because the residual alkali on its surface is reduced and it is more stable when stored in the air.
  • Examples 1-10 can not only improve the structural stability of the material during the charge and discharge process through element doping and tungsten-containing compound coating, but also react with the residual alkali on the surface to form a fast ion conductor.
  • This fast ion conductor coated on the surface of the material can reduce the influence of free residual alkali on the material performance, and can also improve the interface stability of the material, reduce the side reaction with the electrolyte, and improve the cycle stability.

Landscapes

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

Abstract

Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion. Le matériau d'électrode positive de batterie au sodium-ion comprend un substrat d'électrode positive et une couche d'enveloppement, la couche d'enveloppement étant un composé contenant du tungstène recouvrant la surface du substrat d'électrode positive, et le substrat d'électrode positive étant dopé avec un élément M. Le procédé de préparation comprend les étapes suivantes consistant à : mélanger NixFeyMnzMn(OH)2 et un composé contenant du sodium, et fritter le mélange obtenir un matériau NamNixFeyMnzMnO2 ; et mélanger le composé contenant du tungstène et le matériau NamNixFeyMnzMnO2, et calciner le mélange pour obtenir un matériau d'électrode positive comodifié par un revêtement de composé contenant du tungstène et un dopage d'élément M. Le revêtement du composé contenant du tungstène et de l'élément efficace dopé peut réduire une quantité alcaline résiduelle sur la surface du matériau d'électrode positive, ce qui permet d'améliorer complètement la stabilité à l'air de matériaux d'électrode positive de batterie au sodium-ion de type O3, de réduire efficacement la production de gaz, de réduire les réactions secondaires avec des électrolytes, et d'améliorer les performances de cycle des matériaux.
PCT/CN2024/100849 2023-06-25 2024-06-24 Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion Ceased WO2025002026A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202310756708.9A CN116741984A (zh) 2023-06-25 2023-06-25 一种钠离子电池正极材料及制备方法、正极及钠离子电池
CN202310756708.9 2023-06-25

Publications (1)

Publication Number Publication Date
WO2025002026A1 true WO2025002026A1 (fr) 2025-01-02

Family

ID=87904343

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/100849 Ceased WO2025002026A1 (fr) 2023-06-25 2024-06-24 Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion

Country Status (2)

Country Link
CN (1) CN116741984A (fr)
WO (1) WO2025002026A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119943934A (zh) * 2025-01-23 2025-05-06 电子科技大学 一种镁掺杂钠离子电池正极材料、制备方法及应用
CN120784353A (zh) * 2025-09-10 2025-10-14 赣南师范大学 一种o3-p2层状双相钠离子电池正极材料及制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116741984A (zh) * 2023-06-25 2023-09-12 江苏天合储能有限公司 一种钠离子电池正极材料及制备方法、正极及钠离子电池
CN117423825A (zh) * 2023-10-24 2024-01-19 湖北融通高科先进材料集团股份有限公司 一种钠离子电池正极材料及其制备方法和应用
CN117497728B (zh) * 2023-12-04 2024-06-11 湖南美特新材料科技有限公司 一种钠离子电池正极材料及其制备方法
CN117699866A (zh) * 2023-12-14 2024-03-15 江苏天合储能有限公司 一种钠离子电池原位降残碱补钠的方法
CN118833865B (zh) * 2024-09-11 2024-12-24 赣州诺威科技有限公司 前驱体及其制备方法、正极材料及其制备方法、电池
CN119601630B (zh) * 2024-12-04 2026-02-06 深圳为方能源科技有限公司 一种钠离子电池正极材料及其制备方法、钠离子电池和涉电设备
CN119297258B (zh) * 2024-12-06 2025-02-21 湖南美特新材料科技有限公司 一种高电压钠离子正极材料及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654223A (zh) * 2017-01-16 2017-05-10 北京理工大学 一种含钨化合物包覆锂离子电池正极材料的改性方法
CN109244411A (zh) * 2018-09-21 2019-01-18 桑顿新能源科技有限公司 介孔纳米氧化钨包覆的nca正极材料及其制法与锂离子电池
WO2021023313A1 (fr) * 2019-08-06 2021-02-11 湖南杉杉新能源有限公司 Matériau d'anode de batterie au lithium-ion modifié à l'aide de couches de revêtement doubles, et son procédé de préparation
CN115810748A (zh) * 2022-11-16 2023-03-17 深圳市拓邦锂电池有限公司 正极活性材料及其制备方法、正极极片和钠离子电池
CN115863575A (zh) * 2022-12-06 2023-03-28 电子科技大学长三角研究院(湖州) 一种钠离子电池正极材料及其表面包覆方法和应用
CN115881929A (zh) * 2023-03-03 2023-03-31 星恒电源股份有限公司 一种钠离子电池正极材料、其制备方法及应用
CN116111083A (zh) * 2023-03-15 2023-05-12 珠海冠宇电池股份有限公司 正极材料、正极片和钠离子电池
CN116741984A (zh) * 2023-06-25 2023-09-12 江苏天合储能有限公司 一种钠离子电池正极材料及制备方法、正极及钠离子电池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654223A (zh) * 2017-01-16 2017-05-10 北京理工大学 一种含钨化合物包覆锂离子电池正极材料的改性方法
CN109244411A (zh) * 2018-09-21 2019-01-18 桑顿新能源科技有限公司 介孔纳米氧化钨包覆的nca正极材料及其制法与锂离子电池
WO2021023313A1 (fr) * 2019-08-06 2021-02-11 湖南杉杉新能源有限公司 Matériau d'anode de batterie au lithium-ion modifié à l'aide de couches de revêtement doubles, et son procédé de préparation
CN115810748A (zh) * 2022-11-16 2023-03-17 深圳市拓邦锂电池有限公司 正极活性材料及其制备方法、正极极片和钠离子电池
CN115863575A (zh) * 2022-12-06 2023-03-28 电子科技大学长三角研究院(湖州) 一种钠离子电池正极材料及其表面包覆方法和应用
CN115881929A (zh) * 2023-03-03 2023-03-31 星恒电源股份有限公司 一种钠离子电池正极材料、其制备方法及应用
CN116111083A (zh) * 2023-03-15 2023-05-12 珠海冠宇电池股份有限公司 正极材料、正极片和钠离子电池
CN116741984A (zh) * 2023-06-25 2023-09-12 江苏天合储能有限公司 一种钠离子电池正极材料及制备方法、正极及钠离子电池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119943934A (zh) * 2025-01-23 2025-05-06 电子科技大学 一种镁掺杂钠离子电池正极材料、制备方法及应用
CN120784353A (zh) * 2025-09-10 2025-10-14 赣南师范大学 一种o3-p2层状双相钠离子电池正极材料及制备方法

Also Published As

Publication number Publication date
CN116741984A (zh) 2023-09-12

Similar Documents

Publication Publication Date Title
WO2025002026A1 (fr) Matériau d'électrode positive de batterie au sodium-ion, son procédé de préparation, électrode positive et batterie au sodium-ion
CN114790013B (zh) 自补钠的钠离子电池正极活性材料及其制备方法和应用
CN113258060B (zh) 一种钠离子电池高镍层状氧化物材料及其制备方法和应用
CN110380024B (zh) P3结构的钠过渡金属氧化物及其制备方法和钠离子电池
CN101595581B (zh) 非水电解质二次电池用Li-Ni复合氧化物颗粒粉末及其制造方法、非水电解质二次电池
CN111048758B (zh) 一种表面包覆多孔氧化物的正极材料、其制备方法和用途
CN111689528B (zh) 一种三元材料前驱体及其制备方法和用途
CN112164790A (zh) 包覆型锂电池用前驱体、锂电池正极材料及其制备方法
CN103560236B (zh) 氧化铝包覆Li(NixCoyMn1-x-y)O2锂离子电池正极材料的制备方法
CN111082026A (zh) 一种包覆钨酸锂的三元正极材料及其制备方法
CN108649205A (zh) 一种具有变斜率浓度梯度掺杂结构的锂离子电池正极材料及其制备
CN111403729A (zh) 钠离子电池正极材料及其制备方法、钠离子电池
CN104659344A (zh) 一种锂位掺杂与金属氧化物包覆的锂离子电池正极材料及其制备方法
CN115536078B (zh) 一种锂金属氧化物前驱体及其制备方法和应用
KR101013938B1 (ko) 리튬 이차 전지용 양극 활물질, 이의 제조 방법, 및 이를포함하는 리튬 이차 전지
WO2024037261A1 (fr) Procédé de préparation d'un matériau d'électrode positive à base de manganèse riche en lithium de composite lithium-sodium revêtu à double couche
CN106711441B (zh) 一种5v锂离子电池正极材料及其制备方法、一种锂离子电池
CN113363477B (zh) 一种多层包覆三元正极材料的制备方法
CN116364898B (zh) 一种钠离子正极材料及其制备方法与钠离子电池
CN110534737A (zh) 一种高倍率掺杂型镍钴锰三元材料及其制备方法
CN104134797A (zh) 一种高容量富锂正极材料及其制备方法
CN105591099A (zh) 一种钼酸锂表面修饰锂离子电池富镍正极材料及其制备方法
CN114773617A (zh) 一种核壳梯度三元前驱体及其制备方法和应用
JP2012033389A (ja) 正極活物質及びその製造方法並びにリチウムイオン二次電池
CN115172709A (zh) 一种高性能锶掺杂三元钠离子电池正极材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24830671

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE