CN112018358A - Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof - Google Patents

Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof Download PDF

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CN112018358A
CN112018358A CN202010827182.5A CN202010827182A CN112018358A CN 112018358 A CN112018358 A CN 112018358A CN 202010827182 A CN202010827182 A CN 202010827182A CN 112018358 A CN112018358 A CN 112018358A
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张业龙
孙宏阳
周健文
徐晓丹
邱振平
曾庆光
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Wuyi University
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    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a nitrogen-doped/carbon-coated potassium titanate material and a preparation method thereof, wherein the preparation method comprises the following steps: placing silkworm cocoon in NaHCO3Boiling in water solution, washing and drying; dissolving the dried product in CaCl2/C2H5OH/H2Dialyzing and centrifuging the solution O to obtain a silk fibroin solution, and freeze-drying the silk fibroin solution to obtain silk fibroin sponge; dissolving silk fibroin sponge in a solvent to prepare a solution with the weight percentage of 3-30 percent; mixing Ti3C2TxAdding 1-5mol/L potassium hydroxide solution, stirring for 10-40 hrObtaining a mixed solution; centrifuging the mixed solution, discarding the supernatant, washing the filter residue, and drying to obtain a precursor; adding the precursor into the solution obtained in the step (3), magnetically stirring for 1-5 hours, and drying; and placing the dried product in an air atmosphere, heating to 500 ℃ at 300-. The conductivity of the raw material is improved through nitrogen doping/carbon cladding, so that higher rate performance is obtained.

Description

Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a nitrogen-doped/carbon-coated potassium titanate material and a preparation method thereof.
Background
With the continuous deepening of the industrial modernization process, the environmental problem and the energy shortage problem caused by the use process of the traditional fossil energy are increasingly highlighted. In order to meet the strategy of sustainable development, people urgently need to develop green renewable energy sources (solar energy, wind energy, tidal energy and the like), but the renewable energy sources are often unstable and greatly influenced by external environments, for example, the solar energy is influenced by sunshine duration and intensity, and the wind energy and the tidal energy are greatly influenced by seasons. In order to collect the intermittently fluctuating energy, the energy needs to be converted into more stable electric energy for storage, which puts higher demands on large-scale energy storage devices. Among energy storage systems, Lithium Ion Batteries (LIBs) have dominated the market for countless portable electronic devices over the past few decades due to their light weight, high energy density, lack of memory effect, and environmental friendliness. However, lithium, a rare element in the earth's crust, is low in natural abundance and is not uniformly distributed. Moreover, with the growth of the electronic market, the price of lithium salt has greatly increased in this century, and the high price of raw materials is difficult to meet the requirements of the large-scale energy storage market.
Potassium Ion Batteries (PIBs) are considered to be one of the best alternatives to lithium ion batteries due to their abundant resources and comparable energy density. However K+Is of large size
Figure BDA0002636647300000011
This results in two inherent drawbacks: k+Slow diffusion kinetics and large volume change of the intercalation process, resulting in low capacity of the potassium ion battery andthe cycling stability is poor. Therefore, the development of suitable potassium ion battery negative electrode materials is the focus of the development of the potassium ion battery at present.
The titanium-based material is always a powerful competitor of the potassium ion battery cathode due to the advantages of proper oxidation-reduction potential, environmental protection, no toxicity, low cost and the like. Wherein, potassium titanate (K)2Ti4O9) The large interlayer spacing can well adapt to the huge volume change of potassium ions in the embedding and removing processes. However, pure potassium titanate (K)2Ti4O9) The rate and conductivity of the electrolyte are not ideal, which seriously hinders potassium titanate (K)2Ti4O9) The practical application of (1).
Disclosure of Invention
In view of the problems of the prior art, an object of the present invention is to provide a nitrogen-doped/carbon-coated potassium titanate material. The invention also aims to provide a preparation method of the nitrogen-doped/carbon-coated potassium titanate material. Further, the invention provides application of the nitrogen-doped/carbon-coated potassium titanate material, and the nitrogen-doped/carbon-coated potassium titanate material is used as a potassium ion battery negative electrode.
The invention adopts the following technical scheme:
a preparation method of a nitrogen-doped/carbon-coated potassium titanate material comprises the following steps:
(1) placing silkworm cocoon in NaHCO3Boiling the water solution for 30-120 minutes, washing with deionized water and drying;
(2) dissolving the dried product obtained in step (1) in CaCl at 50-80 deg.C, preferably 60-70 deg.C, such as 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C2/C2H5OH/H2O solution for 3 to 10 hours, such as 3 hours, 5 hours, 7 hours, 9 hours, 10 hours, preferably 5 hours;
(3) dialyzing the solution obtained in the step (2) in deionized water for 10-48 hours, preferably 20-40 hours by using a dialysis bag, and centrifuging;
(4) collecting the supernatant centrifuged in the step (3), and freeze-drying to obtain silk fibroin sponge;
(5) dissolving the silk fibroin sponge obtained in the step (4) in a solvent to prepare a solution with the concentration of 3-30 wt%;
(6) mixing Ti3C2TxAdding a potassium hydroxide solution having a concentration of 1 to 5mol/L, such as 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, preferably 3mol/L, followed by stirring for 10 to 40 hours, such as 10 hours, 20 hours, 30 hours, 40 hours;
(7) centrifuging the product obtained in the step (6), discarding the supernatant, cleaning with a cleaning agent, and vacuum-drying to obtain a precursor;
(8) adding the precursor obtained in the step (7) into the solution obtained in the step (5), stirring for 1-5 hours, and drying;
(9) placing the dried product obtained in the step (8) into a corundum crucible, and transferring the corundum crucible into a heating furnace;
(10) heating the heating furnace to 500 ℃ at the temperature rising speed of 3-6 ℃/min, preferably 5 ℃/min in the air atmosphere, for example, 300 ℃, 400 ℃, 500 ℃, preserving heat for 1-5 hours, preferably 3 hours, then heating to 1200 ℃ at the temperature rising speed of 2-4 ℃/min, preferably 3 ℃/min, for example, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, preserving heat for 1-3 hours, and naturally cooling to room temperature;
(11) and collecting the solid in the corundum crucible to obtain the nitrogen-doped/carbon-coated potassium titanate material.
Further, the solvent in step (5) is selected from one or more of formic acid, acetic acid and water.
Further, said NaHCO3The concentration of the aqueous solution is 0.01 to 0.05mol/L, preferably 0.02mol/L, for example 0.01mol/L, 0.03mol/L, 0.05 mol/L.
Further, the CaCl in the step (2)2/C2H5OH/H2The molar ratio of O is preferably 1:2-4: 6-10.
Further, the specification of the dialysis bag in the step (3) is MWCO 2500-.
Further, the freeze-drying time in step (4) is 10 to 36 hours, preferably 24 hours, such as 10 hours, 16 hours, 30 hours, 36 hours.
Further, the cleaning agent is any one or two of water and ethanol. Washing the filter residue in the step (7) by using ultrapure water and absolute ethyl alcohol preferably, and alternately washing the filter residue by using the ultrapure water and the absolute ethyl alcohol for 3-6 times, preferably 3 times.
Further, the temperature of vacuum drying in step (7) is 60-80 ℃, preferably 70 ℃, and the drying time is 4-16 hours, preferably 8 hours, such as 6 hours, 9 hours, 10 hours, 11 hours, 12 hours; the vacuum does not exceed 150Pa, preferably 120Pa, for example 133Pa, 130Pa, 120Pa, 110Pa, 90 Pa.
Further, the mass ratio of the precursor to the silk fibroin in the step (8) can be 1:1-4, preferably 1:2, and optionally 1:1, 1:3, 1: 4.
Further, the drying means in step (8) may be ordinary drying or vacuum drying, the drying temperature may be 50-80 deg.C, preferably 70 deg.C, and the drying time may be 6-12 hours, preferably 8 hours.
Further, the heating furnace in the step (10) is a high-temperature heating furnace, preferably a tube furnace, and optionally a box-type heating furnace.
A potassium ion battery cathode comprises the nitrogen-doped/carbon-coated potassium titanate material prepared by the preparation method.
A potassium ion battery includes the above battery negative electrode.
The invention has the beneficial effects that:
(1) the method takes the silkworm cocoons as the common source of the nitrogen source and the carbon source, the sources of the used raw materials are wide, the cost is low, and the use scenes of the silkworm cocoons are widened.
(2) Compared with the pure potassium titanate, the mixture of the fibroin protein and the potassium titanate can be uniformly coated with nitrogen-doped carbon on the surface of the potassium titanate through heat treatment, the conductivity of the obtained nitrogen-doped/carbon-coated potassium titanate material is greatly improved, and the rate capability and the stability are greatly improved.
Drawings
FIG. 1 is a scanning electron micrograph of a single pure potassium titanate material in comparative example 1;
FIG. 2 is a scanning electron micrograph of a nitrogen-doped/carbon-coated potassium titanate material according to example 1;
FIG. 3 is a graph of rate performance at different current densities for the single potassium titanate material of comparative example 1;
figure 4 is a graph of rate capability at different current densities for the nitrogen-doped/carbon-coated potassium titanate material of example 1.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Wherein the materials are commercially available unless otherwise specified.
Wherein the materials are commercially available unless otherwise specified;
the Ti3C2TxThe granules were purchased from beijing beike science and technology ltd, code BK2020011814, sheet stacking thickness: 1-5 μm, purity: 99%, product application field: energy storage, catalysis, analytical chemistry, and the like.
The method is a conventional method unless otherwise specified.
Nitrogen-doped carbon coating layer: transmission Electron Microscopy (TEM).
And (3) testing the battery performance: respectively mixing an active substance (K2Ti4O9, NC-K2Ti4O9) with conductive carbon black and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, performing vacuum drying at 80 ℃, and slicing to obtain the potassium ion battery negative plate with the diameter of 18 mm. The negative pole piece, the metal potassium foil and the diaphragm (Whatman, GF/F) are assembled into a 2032 type button cell in a glove box, and a Wuhan blue battery test system is utilized to test the battery performance.
The invention provides a preparation method of a nitrogen-doped/carbon-coated potassium titanate material, wherein the synthesis method of the potassium titanate material is shown in the following steps: hydrothermal synthesis and morphology control of momenta titanate [ D ]. university of Hunan university, 2018 ] "
Example 1
A preparation method of a nitrogen-doped/carbon-coated potassium titanate material comprises the following steps:
(1) 5g of silkworm cocoon in 300ml of 0.02mol/L NaHCO3Boiling the water solution for 30 minutes, washing the water solution by deionized water, and drying the water solution;
(2) dissolving the dried product obtained in the step (1) in CaCl with the molar ratio of 1:2:8 at 70 DEG C2/C2H5OH/H2O solution for 3 hours;
(3) dialyzing the solution obtained in the step (2) in deionized water for 12 hours by using an MWCO 3500 specification dialysis bag, and then centrifuging;
(4) collecting the supernatant centrifuged in the step (3), and freeze-drying for 24 hours to obtain silk fibroin sponge;
(5) adding 200mg of the silk fibroin sponge obtained in the step (4) into formic acid to prepare a solution with the concentration of 15 wt%;
(6) mixing Ti3C2TxAdding 1mol/L potassium hydroxide solution, and then stirring for 12 hours;
(7) centrifuging the product obtained in the step (6) at the rotating speed of 4000r/min, discarding the supernatant, alternately cleaning the filter residue for three times by using deionized water and ethanol, and performing vacuum drying at the temperature of 70 ℃ to obtain a precursor;
(8) adding 100mg of the precursor obtained in the step (7) into the solution obtained in the step (5), stirring for 3 hours and drying;
(9) placing the dried product obtained in the step (8) into a corundum crucible, and transferring the corundum crucible into a tubular furnace;
(10) heating the tube furnace to 320 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving heat for 3 hours, then heating to 1000 ℃ at the heating rate of 3 ℃/min, preserving heat for 1.5 hours, and naturally cooling;
(11) and collecting the solid in the corundum crucible to obtain the nitrogen-doped/carbon-coated potassium titanate material.
The reversible capacity of the nitrogen-doped/carbon-coated potassium titanate material of the present example was 243, 207, 175, 133mAh/g at current densities of 100, 200, 500, 1000, 2000mA/g, respectively, and when the current density became 100mA/g, the capacity was restored to 236mAh/g, indicating its excellent rate capability.
Example 2
A preparation method of a nitrogen-doped/carbon-coated potassium titanate material comprises the following steps:
(1) adding 10g silkworm cocoon into 500ml of 0.03mol/L NaHCO3Boiling the water solution for 30 minutes, washing the water solution by deionized water, and drying the water solution;
(2) dissolving the dried product obtained in the step (1) in CaCl with a molar ratio of 1:2:8 at 80 DEG C2/C2H5OH/H2O solution for 2 hours;
(3) dialyzing the solution obtained in the step (2) in deionized water for 24 hours by using an MWCO 3500 specification dialysis bag, and then centrifuging;
(4) collecting the supernatant centrifuged in the step (3), and freeze-drying for 24 hours to obtain silk fibroin sponge;
(5) adding 800mg of the silk fibroin sponge obtained in the step (4) into formic acid to prepare a solution with the concentration of 10 wt%;
(6) mixing Ti3C2TxAdding a potassium hydroxide solution with the concentration of 2mol/L, and then stirring for 8 hours;
(7) centrifuging the product obtained in the step (6) at the rotating speed of 5000r/min, discarding the supernatant, alternately cleaning the filter residue for three times by using deionized water and ethanol, and then carrying out vacuum drying at the temperature of 65 ℃ to obtain a precursor;
(8) adding 200mg of the precursor obtained in the step (7) into the solution obtained in the step (5), stirring for 5 hours and drying;
(9) placing the dried product obtained in the step (8) into a corundum crucible, and transferring the corundum crucible into a tubular furnace;
(10) heating the tube furnace to 300 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving heat for 3 hours, then heating to 900 ℃ at the heating rate of 3 ℃/min, preserving heat for 3 hours, and naturally cooling;
(11) and collecting the solid in the corundum crucible to obtain the nitrogen-doped/carbon-coated potassium titanate material.
The reversible capacity of the nitrogen-doped/carbon-coated potassium titanate material of the embodiment is 258, 212, 183 and 146mAh/g at current densities of 100, 200, 500, 1000 and 2000mA/g, respectively, and when the current density is changed to 100mA/g, the capacity is recovered to 247mAh/g, which shows excellent rate capability.
Example 3
A preparation method of a nitrogen-doped/carbon-coated potassium titanate material comprises the following steps:
(1) 50g of silkworm cocoon in 1000ml of 0.05mol/L NaHCO3Boiling the water solution for 60 minutes, washing the water solution by deionized water, and drying the water solution;
(2) dissolving the dried product obtained in the step (1) in CaCl with a molar ratio of 1:2:8 at 60 DEG C2/C2H5OH/H2O solution for 2 hours;
(3) dialyzing the solution obtained in the step (2) in deionized water for 36 hours by using an MWCO 3500 specification dialysis bag, and then centrifuging;
(4) collecting the supernatant centrifuged in the step (3), and freeze-drying for 36 hours to obtain silk fibroin sponge;
(5) adding 1500mg of the silk fibroin sponge obtained in the step (4) into formic acid to prepare a solution with the concentration of 10 wt%;
(6) mixing Ti3C2TxAdding 3mol/L potassium hydroxide solution, and then stirring for 6 hours;
(7) centrifuging the product obtained in the step (6) at the rotating speed of 4500r/min, discarding the supernatant, alternately cleaning the filter residue for three times by using deionized water and ethanol, and then carrying out vacuum drying at the temperature of 60 ℃ to obtain a precursor;
(8) adding 500mg of the precursor obtained in the step (7) into the solution obtained in the step (5), stirring for 5 hours and drying;
(9) placing the dried product obtained in the step (8) into a corundum crucible, and transferring the corundum crucible into a tubular furnace;
(10) heating the tube furnace to 350 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving heat for 2 hours, then heating to 1100 ℃ at the heating rate of 3 ℃/min, preserving heat for 1 hour, and naturally cooling;
(11) and collecting the solid in the corundum crucible to obtain the nitrogen-doped/carbon-coated potassium titanate material.
The reversible capacity of the nitrogen-doped/carbon-coated potassium titanate material of the embodiment at current densities of 100, 200, 500, 1000 and 2000mA/g is 218, 175, 143 and 116mAh/g respectively, and when the current density is changed to 100mA/g, the capacity is recovered to 203mAh/g, which shows excellent rate capability.
Comparative example 1:
the preparation method of the pure potassium titanate comprises the following steps:
(1) adding potassium hydroxide into a solvent to prepare a potassium hydroxide solution with the concentration of 1 mol/L;
(2) mixing 100mg of Ti3C2TxAdding 80ml of the potassium hydroxide aqueous solution prepared in the step (1), and then stirring at a stirring speed of 600r/min for 8 hours;
(3) centrifuging the product obtained in the step (2) at the rotating speed of 7000r/min, discarding filter residues, and alternately cleaning for 5 times by using ethanol and ultrapure water;
(4) drying the centrifugal product obtained in the step (3) in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain a precursor;
(5) placing the precursor obtained in the step (4) into a corundum crucible, and transferring into a tubular furnace;
(6) heating the tube furnace to 900 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving the heat for 4 hours, and cooling to room temperature;
(7) and collecting the solid in the corundum crucible to obtain the potassium titanate material.
The reversible capacity of the nitrogen-doped/carbon-coated potassium titanate material of the embodiment is 169, 135, 93 and 67mAh/g at current densities of 100, 200, 500 and 1000mA/g, respectively, and when the current density is changed to 100mA/g, the capacity is recovered to 155mAh/g, which shows excellent rate capability.
Table 1: performance testing
Figure BDA0002636647300000061
Figure BDA0002636647300000071
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.

Claims (10)

1. A preparation method of a nitrogen-doped/carbon-coated potassium titanate material is characterized by comprising the following steps:
(1) placing silkworm cocoon in NaHCO3Boiling in water solution for 30-120 min, washing, and drying;
(2) placing the dried product obtained in the step (1) in CaCl2/C2H5OH/H2Heating the O solution at 50-70 ℃ for 3-10 hours to obtain a mixed solution;
(3) dialyzing the mixed solution obtained in the step (2) for 12-36 hours, and centrifuging to remove impurities to obtain a silk fibroin solution;
(4) freeze-drying the silk fibroin solution to obtain silk fibroin sponge;
(5) dissolving silk fibroin sponge in a solvent to prepare a solution with the weight percentage of 3-30 percent;
(4) mixing Ti3C2TxAdding 1-5mol/L potassium hydroxide solution, and stirring for 10-40 hours to obtain mixed solution;
(5) centrifuging the mixed solution, discarding the supernatant, washing the filter residue, and drying to obtain a precursor;
(6) adding the precursor into the solution obtained in the step (3), magnetically stirring for 1-5 hours, and drying;
(7) and (3) placing the dried product obtained in the step (6) in an air atmosphere, heating to 500 ℃ at the heating rate of 3-6 ℃/min, preserving heat for 1-5 hours, then heating to 1200 ℃ at the heating rate of 2-4 ℃/min, preserving heat for 1-3 hours, cooling, and collecting to obtain the nitrogen-doped/carbon-coated potassium titanate material.
2. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein the solvent in the step (3) is one or more selected from formic acid, acetic acid and water.
3. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein said NaHCO is used in step (1)3The concentration of the aqueous solution is 0.01-0.05 mol/L.
4. The method of claim 1, wherein the CaCl in step (2) is added to the nitrogen-doped/carbon-coated potassium titanate material2/C2H5OH/H2The molar ratio of O is 1:2-4: 6-10.
5. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein the dialysis time in the step (2) is 12-36 hours.
6. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein the freeze-drying time in the step (2) is 12-36 hours.
7. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein the concentration of the potassium hydroxide solution in the step (4) is 1-5 mol/L.
8. The method for preparing nitrogen-doped/carbon-coated potassium titanate material according to claim 1, wherein the mass ratio of the precursor in the step (6) to the silk fibroin is 1: 1-4.
9. A potassium ion battery negative electrode, characterized in that it comprises the nitrogen-doped/carbon-coated potassium titanate material produced by the production method according to any one of claims 1 to 8.
10. A potassium ion battery comprising the battery negative electrode of claim 9.
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CN115050945A (en) * 2022-07-15 2022-09-13 湖北工业大学 Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material

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