CN111900401A - Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite - Google Patents

Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite Download PDF

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CN111900401A
CN111900401A CN202010723050.8A CN202010723050A CN111900401A CN 111900401 A CN111900401 A CN 111900401A CN 202010723050 A CN202010723050 A CN 202010723050A CN 111900401 A CN111900401 A CN 111900401A
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lithium battery
positive electrode
electrode material
nitrogen
tungsten
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CN111900401B (en
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史家远
苟敏涛
吴宁宁
黄鹏
唐康康
胡锦飞
陈晓涛
石斌
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Guizhou Meiling Power Supply Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • H01M10/0422Cells or battery with cylindrical casing
    • H01M10/0427Button cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625Carbon or graphite
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    • H01ELECTRIC ELEMENTS
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
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Abstract

The invention belongs to the technical field of lithium battery anode material manufacturing, and particularly relates to a method for coating a tungsten oxide and nitrogen-doped carbon composite anode material of a lithium battery.

Description

Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite
Technical Field
The invention belongs to the technical field of lithium battery positive electrode material manufacturing, and particularly relates to a method for coating a tungsten oxide and nitrogen-doped carbon composite positive electrode material of a lithium battery.
Background
Lithium iron phosphate is one of the most widely used electrode materials of lithium batteries at present. This is mainly due to the good cycling stability brought about by the olivine crystal structure of lithium iron phosphate. On the other hand, lithium iron phosphate does not contain expensive and environmental-polluting components such as cobalt element, and thus has significant advantages in material preparation and waste disposal (chem.eng.j.2020,379, 122371). However, lithium iron phosphate also has many inherent problems, which mainly include the problems of poor rate performance of lithium iron phosphate caused by weak electron conductivity and slow lithium ion transport performance of lithium iron phosphate (Energy environ. sci.2012,5,5163). At present, solutions to these problems mainly include micronization or nanocrystallization of lithium iron phosphate particles, doping modification of metal or nonmetal elements, and surface coating modification of lithium iron phosphate by carbon and conductive polymers (j.power Sources 2010,195,3680).
Tungsten element has been used in modification of lithium battery positive electrode materials as a commonly used doping element (patent CN111082026A), and can improve electrochemical cycling stability of the positive electrode material without affecting the capacity of the positive electrode material (j. Tungsten oxide is also used in coating modification of lithium battery positive electrode materials. Tungsten oxide can be used as an overcharge resistant material to inhibit thermal runaway of a battery of a lithium battery and improve the electrochemical stability of a positive electrode material (patent CN 110600678A); a tungsten-containing compound is selected as a coating substance, and the coating layer can effectively inhibit side reaction between electrolyte and a positive electrode material, can also inhibit dissolution of transition metal in the material and the like, and effectively enhances the cycle stability, the cycle performance under high rate and the like of the material (patent CN 106935840A); however, the tungsten oxide coating cannot improve the conductivity of the cathode material, and although the lithium iron phosphate cathode material coated by the tungsten carbide shell prepared by the invention is disclosed to have excellent rate performance (patent CN105633362A), the manufacturing process uses a method of plasma surrounding with high chemical reaction activity, which is not beneficial to industrial production, so that a new coating modification method needs to be developed to achieve the purpose of improving the electrochemical stability and conductivity of the cathode material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for coating a positive electrode material of a lithium battery by compounding tungsten oxide and nitrogen-doped carbon.
The method is realized by the following technical scheme:
a method for coating a positive electrode material of a lithium battery by compounding tungsten oxide and nitrogen-doped carbon comprises the steps of forming a coating layer on the surface of the positive electrode material of the lithium battery by adopting polymerization of a carbon precursor and precipitation of the tungsten precursor, and then realizing solidification and bonding of the coating layer through a calcining process.
A method for coating a positive electrode material of a lithium battery by tungsten oxide and nitrogen-doped carbon comprises the following steps:
1) preparing materials: dissolving soluble tungstate in water to prepare a tungstate solution; dissolving dopamine in deionized water to prepare a dopamine solution;
2) the tungsten and carbon precursor is coated on the lithium battery anode material: dispersing a lithium battery positive electrode material into a tungstate solution, adding a dopamine solution, and stirring to prepare a mixed reaction solution; centrifuging, washing and drying the obtained product to obtain the tungsten and carbon precursor co-coated lithium battery anode material;
3) mixing materials: and calcining the dried tungsten and carbon precursor under the protection of protective gas to obtain the tungsten and carbon precursor co-coated lithium battery anode material.
The soluble tungstate is any one or a mixture of sodium tungstate, potassium tungstate, sodium phosphotungstate, ammonium paratungstate and ammonium metatungstate.
The stirring process conditions are as follows: the temperature is 5-70 ℃, and the time is 3-40 h.
The lithium battery anode material is any one or a mixture of more of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobaltate, molybdenum trioxide and lithium manganate.
The positive electrode material in the mixed reaction liquid: tungstate: the molar ratio of dopamine is 1200:1:40 to 1200:10: 200; dopamine: the molar ratio of the tungstate is 4-200.
The protective gas is any one or a mixture of nitrogen and argon.
The calcination comprises the following process conditions: the temperature is 300-600 ℃, and the calcining time is 5-20 h.
Has the advantages that:
the method has the characteristics of low cost, low energy consumption and simple operation, and the lithium battery anode material prepared by the method has excellent electronic conductivity and electrochemical stability.
According to the method, the method that the polymerization of the carbon precursor and the precipitation of the tungsten precursor are mutually promoted is adopted, and calcination is combined, so that the tungsten oxide and nitrogen-doped carbon co-coated lithium battery anode material is realized, a weak alkaline buffer solution system required by coating dopamine on the surface of the anode material is not required, the pH value of a reaction system is not required to be adjusted, the cost for purchasing a reagent is saved, the pollution of an organic reagent is prevented, and more importantly, the operation is simplified and the control requirement is reduced.
The novel positive electrode material is prepared by coating the positive electrode material of the lithium battery with the nitrogen-doped carbon and the tungsten oxide, and the performance improvement of the electronic conductivity and the electrochemical stability of the positive electrode material of the lithium battery is realized.
The inventor realizes better bonding performance with the lithium battery anode material by controlling the concentration of the precursor reaction, is beneficial to curing, and is also beneficial to reducing the requirements of calcination temperature and time, thereby being beneficial to reducing energy consumption. In general, the calcination temperature of the positive electrode material of the nitrogen-doped carbon-coated lithium battery is 650-: the grain diameter of the sample K1 obtained at 600 ℃ is not uniform and the agglomeration phenomenon is serious; the sample K2 obtained at 650 ℃ and the sample K3 obtained at 700 ℃ have uniform particle size distribution, small particle size, no obvious agglomeration phenomenon and similar particle shapeSpherical, which is advantageous for an increase in the bulk density of the material; the sample K4 obtained at 750 ℃ has non-uniform particle size and shape, some are spherical-like and some are polygonal, because of aggregation of some small particles due to higher calcination temperature. For lithium iron phosphate, the raw materials cannot be subjected to chemical reaction at a lower temperature, and cannot synthesize a single-phase LEP material, but the reaction is promoted by controlling the concentration of soluble tungstate and dopamine solution, so that the calcination temperature is reduced, and good calcination is realized at the temperature of 600 ℃ below 300-; meanwhile, the calcination time is controlled, so that the crystallization degree is complete, the generated particles are uniformly distributed and uniform in size, and Fe is prevented2The generation of P particles prevents the change of the grain growth direction of the product, and effectively avoids the phenomena of grain enlargement and aggregation.
Drawings
FIG. 1: x-ray diffraction patterns of the lithium iron phosphate before and after coating; wherein
FIG. 2: scanning electron micrographs of lithium iron phosphate before (a) and after (b) coating;
FIG. 3: the electrochemical impedance spectrum of the CR2025 button cell assembled by the lithium iron phosphate before and after coating is adopted;
FIG. 4: the rate capability of the CR2025 button cell assembled by the lithium iron phosphate before and after coating is adopted.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
Dissolving ammonium metatungstate in 19mL of water, and then dispersing 1.9 g of lithium iron phosphate in the ammonium metatungstate solution; dissolving dopamine in 1mL of deionized water, and adding the dopamine into a dispersion liquid containing lithium iron phosphate and ammonium metatungstate to prepare a mixed reaction liquid, wherein the amount of an ammonium metatungstate substance in the mixed reaction liquid is 0.024mmol, and the amount of a dopamine substance in the mixed reaction liquid is 1.26 mmol;
stirring the mixed reaction solution at 25 ℃ for 24 hours, centrifuging, washing and drying the obtained product to obtain a tungsten and carbon precursor co-coated lithium iron phosphate material;
calcining the dried tungsten and carbon precursor co-coated lithium iron phosphate anode material for 6 hours under the conditions of argon protection and the calcining temperature of 500 ℃ to obtain a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate anode material;
the method comprises the steps of assembling a CR2025 type button cell by taking a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate material as a positive electrode material, and carrying out charge-discharge test under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), wherein the discharge capacity is 123.8 mAh/g;
the inventors perform performance testing on example 1, specifically as follows:
fig. 1 is an X-ray diffraction pattern of lithium iron phosphate before and after coating, which can be seen from X-ray diffraction: the peak type and the peak wave length in the X-ray diffraction pattern before and after the coating of the lithium iron phosphate are basically consistent, which indicates that no impurity peak is generated, the spectrum peak is sharp, which indicates that the crystallinity is excellent, and the added tungstate and dopamine do not influence the crystal structure of the lithium iron phosphate;
fig. 2 is scanning electron micrographs of lithium iron phosphate before (a) and after (b) coating, and it can be seen from the SEM images that: the shape of the lithium iron phosphate particles after load wrapping is similar to a sphere.
Fig. 3 is an electrochemical impedance spectrum of a CR2025 button cell assembled with lithium iron phosphate before and after coating, which is known from the electrochemical impedance spectrum: the radius of the coated lithium iron phosphate is reduced, which shows that the speed of lithium ions reaching the surface of the electrode through the transmission of the electrolyte is increased, and the ion conductivity after coating is higher than that before coating because the slope after coating is lower than that before coating.
Fig. 4 shows the rate performance of a CR2025 button cell assembled by using the lithium iron phosphate before and after coating, and tests the discharge specific capacity fading condition of the lithium iron phosphate before and after coating under different rate conditions, wherein the coated lithium iron phosphate circulates 10 times under the rate of 0.1C, 0.2C, 0.5C, and 1C, the discharge specific capacity fading is not obvious, and the average values are: 156.3mA · h/g, 155.1mA · h/g, 149.7mA · h/g, 123.8mA · h/g.
Example 2
Dissolving ammonium paratungstate in 19mL of water, and then dispersing 1.9 g of lithium iron phosphate in the ammonium paratungstate solution; dissolving dopamine in 1mL of deionized water, and adding the dopamine into a dispersion liquid containing lithium iron phosphate and ammonium paratungstate to prepare a mixed reaction liquid, wherein the amount of an ammonium paratungstate substance in the mixed reaction liquid is 0.01mmol, and the amount of a dopamine substance in the mixed reaction liquid is 0.44 mmol;
stirring the mixed reaction solution at 5 ℃ for 5 hours, centrifuging, washing and drying the obtained product to obtain a tungsten and carbon precursor co-coated lithium iron phosphate material;
calcining the dried tungsten and carbon precursor co-coated lithium iron phosphate anode material for 7h under the conditions of argon protection and the calcining temperature of 300 ℃ to obtain a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate anode material;
the method comprises the steps of assembling a CR2025 type button cell by taking a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate material as a positive electrode material, and carrying out charge-discharge tests under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), wherein the discharge capacity is 122.6 mAh/g.
Example 3
Dissolving sodium phosphotungstate in 19mL of water, and then dispersing 1.9 g of lithium iron phosphate in the sodium phosphotungstate solution; dissolving dopamine in 1mL of deionized water, and adding the dopamine into a dispersion liquid containing lithium iron phosphate and sodium phosphotungstate to prepare a mixed reaction liquid, wherein the amount of an ammonium paratungstate substance in the mixed reaction liquid is 0.01mmol, and the amount of a dopamine substance in the mixed reaction liquid is 0.55 mmol;
stirring the mixed reaction solution at 68 ℃ for 30h, centrifuging, washing and drying the obtained product to obtain a tungsten and carbon precursor co-coated lithium iron phosphate material;
calcining the dried tungsten and carbon precursor co-coated lithium iron phosphate anode material for 18h under the conditions of argon protection and the calcining temperature of 420 ℃ to obtain a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate anode material;
the method comprises the steps of assembling a CR2025 type button cell by taking a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate material as a positive electrode material, and carrying out charge-discharge tests under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), wherein the discharge capacity is 124.2 mAh/g.
Example 4
Dissolving sodium tungstate in 19mL of water, and then dispersing 1.9 g of lithium iron phosphate in the sodium tungstate solution; dissolving dopamine in 1mL of deionized water, and adding the dopamine into a dispersion liquid containing lithium iron phosphate and sodium tungstate to prepare a mixed reaction liquid, wherein the amount of a sodium tungstate substance in the mixed reaction liquid is 0.018mmol, and the amount of a dopamine substance in the mixed reaction liquid is 0.4 mmol;
stirring the mixed reaction solution at 20 ℃ for 3h, centrifuging, washing and drying the obtained product to obtain a tungsten and carbon precursor co-coated lithium iron phosphate material;
calcining the dried tungsten and carbon precursor co-coated lithium iron phosphate anode material for 20h under the conditions of argon protection and the calcining temperature of 600 ℃ to obtain a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate anode material;
the method comprises the steps of assembling a CR2025 type button cell by taking a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate material as a positive electrode material, and carrying out charge-discharge tests under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), wherein the discharge capacity is 123.5 mAh/g.
Example 5
Dissolving potassium tungstate in 19mL of water, and then dispersing 1.9 g of lithium iron phosphate in a potassium tungstate solution; dissolving dopamine in 1mL of deionized water, and adding the dopamine into a dispersion liquid containing lithium iron phosphate and potassium tungstate to prepare a mixed reaction liquid, wherein the amount of a potassium tungstate substance in the mixed reaction liquid is 0.09mmol, and the amount of a dopamine substance in the mixed reaction liquid is 1.1 mmol;
stirring the mixed reaction solution at 10 ℃ for 4h, centrifuging, washing and drying the obtained product to obtain a tungsten and carbon precursor co-coated lithium iron phosphate material;
calcining the dried tungsten and carbon precursor co-coated lithium iron phosphate anode material for 5 hours under the conditions of argon protection and the calcining temperature of 550 ℃ to obtain a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate anode material;
the method comprises the steps of assembling a CR2025 type button cell by taking a tungsten oxide and nitrogen-doped carbon co-coated lithium iron phosphate material as a positive electrode material, and carrying out charge-discharge tests under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), wherein the discharge capacity is 126.1 mAh/g.
The method of example 5 is used for coating the lithium battery anode material, then the CR2025 button cell is assembled, the charging and discharging tests are carried out under the conditions of 30 ℃, 2.5-4.2V and 1C (170mA/g), and the discharging capacity is shown in Table 1;
TABLE 1
Figure BDA0002600713150000081
Figure BDA0002600713150000091

Claims (9)

1. A method for coating a positive electrode material of a lithium battery by compounding tungsten oxide and nitrogen-doped carbon is characterized in that polymerization of a carbon precursor and precipitation of the tungsten precursor are adopted to form a coating layer on the surface of the positive electrode material of the lithium battery, and then solidification and bonding of the coating layer are realized through a calcining process.
2. The method for preparing the positive electrode material of the tungsten oxide and nitrogen-doped carbon composite coated lithium battery as claimed in claim 1, wherein the method comprises the following steps:
1) preparing materials: dissolving soluble tungstate in water to prepare a tungstate solution; dissolving dopamine in deionized water to prepare a dopamine solution;
2) the tungsten and carbon precursor is coated on the lithium battery anode material: dispersing a lithium battery positive electrode material into a tungstate solution, adding a dopamine solution, and stirring to prepare a mixed reaction solution; centrifuging, washing and drying the obtained product to obtain the tungsten and carbon precursor co-coated lithium battery anode material;
3) mixing materials: and calcining the dried tungsten and carbon precursor under the protection of protective gas to obtain the tungsten and carbon precursor co-coated lithium battery anode material.
3. The method of claim 2, wherein the soluble tungstate is any one or a mixture of sodium tungstate, potassium tungstate, sodium phosphotungstate, ammonium paratungstate and ammonium metatungstate.
4. The method for preparing the positive electrode material of the tungsten oxide and nitrogen-doped carbon composite coated lithium battery as claimed in claim 2, wherein the stirring process comprises the following steps: the temperature is 5-70 ℃, and the time is 3-40 h.
5. The method according to claim 2, wherein the positive electrode material of the lithium battery is any one or a mixture of lithium iron phosphate, lithium manganese phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, molybdenum trioxide and lithium manganese oxide.
6. The method for preparing the positive electrode material of the tungsten oxide and nitrogen-doped carbon composite coated lithium battery as claimed in claim 2, wherein the positive electrode material in the mixed reaction solution: tungstate: the molar ratio of dopamine is 1200:1:40 to 1200:10: 200.
7. The method of claim 2, wherein the protective gas is any one of nitrogen and argon or a mixture thereof.
8. The method for preparing the positive electrode material of the tungsten oxide and nitrogen-doped carbon composite coated lithium battery as claimed in claim 2, wherein the calcination comprises the following process conditions: the temperature is 300-600 ℃, and the calcining time is 5-20 h.
9. The method of claim 2, wherein the ratio of dopamine in the mixed reaction solution: the molar ratio of the tungstate is 4-200.
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