CN114530598A - Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof - Google Patents

Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof Download PDF

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CN114530598A
CN114530598A CN202210023772.1A CN202210023772A CN114530598A CN 114530598 A CN114530598 A CN 114530598A CN 202210023772 A CN202210023772 A CN 202210023772A CN 114530598 A CN114530598 A CN 114530598A
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citrate
nitrogen
negative electrode
oxygen
electrode material
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孙志鹏
鲁晓怡
吴胜
彭瀚东
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Guangdong University of Technology
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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
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of battery materials, and particularly relates to a nitrogen-oxygen-sulfur doped carbon negative electrode material and a preparation method and application thereof. The nitrogen-oxygen-sulfur doped material obtained by the preparation method has rich defect sites and pore channel structures, and is beneficial to improving the coulombic efficiency and the cycle stability of the first circle of the potassium ion battery when being used as a negative electrode material; the adopted raw materials are wide in source, cheap and easy to obtain; the preparation method is simple, mild in condition and beneficial to large-scale production.

Description

Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials. More particularly, relates to a nitrogen-oxygen-sulfur doped carbon negative electrode material, and a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely used in the fields of mobile electronic devices, electric vehicles and the like, but the shortage of lithium sources on the earth and the rising of lithium prices in the global area seriously affect the application of the lithium batteries. Therefore, the energy storage industry urgently needs to develop a novel energy storage device to replace a lithium ion battery and realize efficient and cheap energy storage. Potassium has the advantages of abundant resource reserves, no regional limitation and relatively low price, and is gradually concerned and researched in the electrochemical field. In thatIn carbonate type electrolytes, K+Standard redox potential of/K (-2.88V vs SHE) compared to Li+Li (-2.79V vs SHE) and Na+The voltage of the potassium ion battery is lower (-2.56V vs SHE), which means that the potassium ion battery has higher working voltage in a certain voltage range, and the potassium ion battery has a faster ion diffusion rate in the electrolyte because the interaction between the solvent and the anion in the electrolyte and the potassium ion is weaker than the interaction between the anion and the lithium ion, so that the potassium ion battery is researched by extensive researchers. The negative electrode material in the potassium ion battery has a large influence on the performance of the potassium ion battery.
In the negative electrode material of the potassium ion battery researched at present, mainly a carbon material is used, and the negative electrode material has the advantages of good conductivity, good flexibility and low intercalation voltage platform (more than or equal to 0.2V vs K)+and/K), but the carbon material has lower specific capacity, low first coulombic efficiency and poorer rate capability. In order to overcome the defects of low specific capacity, low first coulombic efficiency and poor rate capability of a carbon material, nonmetal heteroatoms are often doped in the carbon material, for example, Liu and the like synthesize nitrogen-doped soft carbon, the long-cycle stability of the nitrogen-doped soft carbon is improved to a certain extent, and 1 A.g-1The capacity retention rate is 85.5% after the current density is cycled for 500 circles, but a great space is still provided for improvement from practical application; and the first turn of coulombic efficiency is low, only 30.9% (Liu C, Xiao N, Li H, et al. Nitrogen-large soft carbon frame work build of well-interconnected nanoparticles-on batteries anode [ J].Chemical Engineering Journal,2020,382:121759.)。
Disclosure of Invention
The invention aims to solve the technical problems that the long cycle stability of the conventional potassium ion battery cathode material needs to be further improved and the initial coulombic efficiency is low, and provides a preparation method of a nitrogen-oxygen-sulfur doped carbon cathode material.
The invention aims to provide a nitrogen-oxygen-sulfur doped carbon negative electrode material.
The invention also aims to provide application of the nitrogen-oxygen-sulfur doped carbon negative electrode material in preparation of a potassium ion battery negative electrode material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a nitrogen-oxygen-sulfur doped carbon negative electrode material comprises the following steps:
uniformly mixing citrate and an organic compound containing N and S, carrying out heat treatment at 400-900 ℃ in an inert gas atmosphere, and cleaning to obtain the product;
the organic compound containing N and S is one or more of thiourea, melamine, dicyanodiamine or trithiocyanuric acid.
The invention creatively adopts citrate which is simple and easy to obtain as an oxygen source, a carbon source and an in-situ template agent. The citrate is heated and decomposed in the heat treatment process to generate a large amount of oxygen, and the oxygen element is doped in the carbon material to improve the wettability of the carbon material; the citrate partial structure is heated and decomposed to generate alkaline carbonate in situ and release carbon dioxide, and the alkaline carbonate and the carbon dioxide have an activating effect on the carbon material, so that a microporous structure is formed.
Meanwhile, organic components of citrate are pyrolyzed with organic compounds containing N and S in the heat treatment process to form a carbon layer, the citrate is decomposed by heating to generate carbonate in situ to serve as a template to be wrapped in the carbon layer, the carbon layer grows along the template, the carbonate template is removed by deionized water or dilute acid, and the carbon layer after the template is removed forms a unique three-dimensional stacked structure, namely the nitrogen-oxygen-sulfur triple-doped carbon cathode material.
Moreover, when the organic compound containing N and S is heated and decomposed, abundant heteroatom elements (such as sulfur and nitrogen elements) are provided, and the heteroatom elements are doped into the carbon material, so that the carbon material is promoted to generate abundant defect sites, the interlayer spacing of the carbon material is enlarged, and the electronic structure of the carbon material is adjusted, so that the first-turn coulomb efficiency and the cycle stability of the potassium ion battery are improved.
In addition, the citrate and the organic compound containing N and S are blended and pyrolyzed in one step to prepare the nitrogen-oxygen-sulfur doped carbon cathode material, so that the method is simple and convenient to operate, simple in process flow, high in economic benefit and suitable for large-scale production.
Further, the citrate is one or more of lithium citrate, potassium citrate, sodium citrate, potassium sodium citrate, ferric citrate, cupric citrate, magnesium citrate, ammonium citrate and the citrate hydrate.
Preferably, the citrate is potassium citrate, sodium citrate or potassium sodium citrate.
Further, the organic compound containing N and S is thiourea, melamine or dicyanodiamine.
Further, the temperature of the heat treatment is 450-700 ℃.
Preferably, the temperature of the heat treatment is 500 ℃.
Further, the time of the heat treatment is 30-360 min.
Preferably, the time of the heat treatment is 30-240 min.
More preferably, the time of the heat treatment is 60 min.
Furthermore, the heating rate of the heat treatment is 1-10 ℃/min.
Preferably, the heating rate of the heat treatment is 1-5 ℃/min.
More preferably, the temperature increase rate of the heat treatment is 3 ℃/min.
Furthermore, the mass ratio of the citrate to the organic compound containing N and S is 1 (0.05-2).
Preferably, the mass ratio of the citrate to the organic compound containing N and S is 1 (0.1-2).
Further, the inert gas comprises nitrogen and argon.
Further, the method for uniformly mixing is ball milling.
Preferably, the rotation speed of the ball milling is 100-900 r/min.
More preferably, the rotation speed of the ball milling is 300-600 r/min.
Most preferably, the rotation speed of the ball mill is 450 r/min.
Preferably, the ball milling time is 10-60 min.
More preferably, the ball milling time is 20-45 min.
Most preferably, the time of the ball milling is 30 min.
Under the selection conditions of the reaction raw materials and the ball milling rotation speed, the reactants can be uniformly mixed, so that the chemical environment of the reactants is uniform in the heat treatment process, and the distribution of sulfur elements in the product obtained by the reaction is uniform.
Further, the preparation method also comprises the steps of washing and drying after the heat treatment.
Preferably, the washing solution is dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid or deionized water.
More preferably, the washing solution is dilute sulfuric acid, dilute hydrochloric acid, or deionized water.
Most preferably, the washing solution is deionized water.
The invention further provides a nitrogen-oxygen-sulfur doped carbon negative electrode material which is prepared by the preparation method.
The invention further protects the application of the nitrogen-oxygen-sulfur doped carbon negative electrode material in the preparation of the negative electrode material of the potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the nitrogen-oxygen-sulfur doped material obtained by the preparation method has rich defect sites and pore channel structures, and is beneficial to improving the coulombic efficiency and the cycle stability of the first circle of the potassium ion battery when being used as a negative electrode material; the adopted raw materials have wide sources, are cheap and are easy to obtain; the preparation method is simple, mild in condition and beneficial to large-scale production.
Drawings
Fig. 1 shows the micro-morphology of the nitrogen-oxygen-sulfur doped carbon cathode material prepared in example 1 under a field emission Scanning Electron Microscope (SEM).
Fig. 2 is an element distribution diagram (EDS) of the nitrogen-oxygen-sulfur-doped carbon anode material prepared in example 1 of the present invention.
Fig. 3 is an X-ray diffraction pattern (XRD) of the nitrogen oxygen sulfur doped carbon negative electrode material prepared in example 1 of the present invention.
Fig. 4 is a raman spectrometer diagram of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention.
Fig. 5 shows the rate capability of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention under different current densities.
FIG. 6 shows the first coulomb efficiency of the N-O-S doped carbon negative electrode material prepared in example 1 of the present invention at 1 A.g-1Long cycle performance of 1000 cycles at current density.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 preparation method of nitrogen-oxygen-sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing sodium citrate and thiourea with the mass ratio of 1:1 at the rotating speed of 450r/min for 30min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of a nitrogen atmosphere, and then carrying out heat treatment on the precursor for 60min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 2 preparation method of nitrogen-oxygen-sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing potassium citrate and thiourea with the mass ratio of 10:1 at the rotating speed of 450r/min for 30min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 800 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen atmosphere, and then carrying out heat treatment on the precursor for 60min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 3 preparation method of nitrogen-oxygen-sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing sodium citrate and melamine with the mass ratio of 5:1 at the rotating speed of 300r/min for 30min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 600 ℃ at a heating rate of 10 ℃/min under the protection of a nitrogen atmosphere, and then carrying out heat treatment on the precursor for 150min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 by using dilute sulfuric acid, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 4 preparation method of nitrogen-oxygen-sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing potassium sodium citrate and dicyanodiamide in a mass ratio of 15:1 at a rotating speed of 600r/min for 60min at room temperature by using a ball milling method to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 700 ℃ at a heating rate of 1 ℃/min under the protection of a nitrogen atmosphere, and then carrying out heat treatment on the precursor for 120min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 by using dilute hydrochloric acid, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 5 preparation method of nitrogen, oxygen and sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing sodium citrate and thiourea with the mass ratio of 20:1 at the rotating speed of 300r/min for 45min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 900 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and then carrying out heat treatment on the precursor for 360min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Comparative example 1: preparation method of nitrogen-oxygen-sulfur doped carbon negative electrode material
S1, uniformly ball-milling and mixing citric acid and thiourea with a mass ratio of 1:1 at a rotating speed of 450r/min for 30min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of a nitrogen atmosphere, and then carrying out heat treatment on the precursor for 60min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
In step S1, the sodium citrate of example 1 is replaced by the citric acid of comparative example, and during the pyrolysis process, the citric acid is used as the oxygen-containing carbon source only, and no alkaline carbonate is generated during decomposition, so the product has less pore structure.
Comparative example 2: preparation method of carbon negative electrode material
S1, uniformly ball-milling and mixing sodium citrate at the rotating speed of 450r/min for 30min by a ball milling method at room temperature to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of a nitrogen atmosphere, and then carrying out heat treatment on the precursor for 60min to obtain a pyrolysis product;
and S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, then performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Compared with the example 1, the organic compound containing N and S is not added in the step S1, and the product has fewer defect sites and fewer active sites.
Characterization test:
and (3) testing by a scanning electron microscope: the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in the example 1 is subjected to a Scanning Electron Microscope (SEM) test. As shown in FIG. 1, the prepared nitrogen-oxygen-sulfur-doped carbon negative electrode material is formed by aggregating small particles with the average particle size of 176nm, and as can be seen from FIG. 2, N, O, S elements in the nitrogen-oxygen-sulfur-doped carbon negative electrode material are uniformly doped into the carbon material, and the element dispersibility is proved to be good.
X-ray diffraction testing: phase analysis was performed on the nitrogen oxygen sulfur-doped carbon anode material prepared in example 1 using an X-ray diffractometer. As a result, as shown in fig. 3, two broad diffraction peaks appear near 25.8 ° and 43.8 ° of 2 θ, which correspond to the (002) crystal plane peak and the (101) crystal plane peak of the nitrogen-oxygen-sulfur-doped carbon negative electrode material, respectively, but the two diffraction peaks are broad, which indicates that the prepared material has a high degree of disorder, and the product is in an amorphous state.
And (3) Raman spectrum testing: the nitrogen oxygen sulfur doped carbon negative electrode material prepared in example 1 was subjected to chemical composition analysis using a raman spectrometer. The results are shown in FIG. 4, at 1350cm-1And 1580cm-1Two standard peaks (D peak and G peak) belonging to nitrogen-oxygen-sulfur doped carbon cathode material appear nearby, the peak shape is wider and not sharp, and the peak shape is ID/IG0.99, which proves that the material contains more defect sites and has lower graphitization degree.
And (3) electrochemical performance testing:
the nitrogen-oxygen-sulfur-doped carbon negative electrode material is applied to a potassium ion half-cell and can be assembled by means of the prior art, a CR2032 button-type cell shell is used as a shell, a metal potassium sheet is used as a negative electrode, the nitrogen-oxygen-sulfur-doped carbon negative electrode material, carbon black and sodium carboxymethyl cellulose copper foil are loaded to be used as a positive electrode (the mass ratio of the nitrogen-oxygen-sulfur-doped carbon negative electrode material to the carbon black to the sodium carboxymethyl cellulose is 8:1:1), 1M potassium bis (fluorosulfonyl imide) (KFSI) ester electrolyte (a composite solvent with the volume ratio of ethylene carbonate to diethyl carbonate being 1:1) is used as an electrolyte, and a glass fiber diaphragm is used as a cell diaphragm.
The nitrogen-oxygen-sulfur doped carbon negative electrode material is used as a potassium ion half-cell negative electrode, and the electrochemical performance of the potassium ion half-cell negative electrode can be tested by using the prior art means.
When the nitrogen-oxygen-sulfur-doped carbon negative electrode material prepared in each example and each comparative example is used as a potassium ion battery negative electrode, the first-turn coulombic efficiency is 1A-g-1The average capacity decay rate per cycle after 500 cycles at current density is shown in table 1:
table 1: the first-turn coulombic efficiency of each example and each comparative example when the lithium ion battery negative electrode is applied to the potassium ion battery is 1 A.g-1Average capacity attenuation rate per cycle after 500 cycles under current density
Figure BDA0003463583040000071
As can be seen from table 1, the electrochemical performance of the nitrogen-oxygen-sulfur-doped carbon negative electrode material prepared in each example is better than that of the comparative example, wherein the nitrogen-oxygen-sulfur-doped carbon negative electrode material prepared in example 1 has the best performance, the coulombic efficiency in the first cycle reaches 51%, and the average capacity attenuation rate per cycle after 500 cycles is only 0.0457%.
In the comparative example 1, citric acid is selected to react with thiourea, the citric acid is only used as an oxygen-containing carbon source in the reaction process, no alkaline carbonate is generated in the pyrolysis process, a pore structure cannot be formed in the carbon material, the carbon material cannot be activated to form micropores, so that the electrolyte cannot be fully infiltrated, the contact between an internal material and the electrolyte is poor, and the potassium ion diffusion is influenced. Meanwhile, in the electrochemical circulation process, the electrode material is easy to break and fall off, the electrochemical performance is poor, and after 100 cycles of circulation, the electrode material is subjected to irreversible hard inactivation.
Comparative example 2 selects sodium citrate to be directly carbonized, organic compounds containing N and S are not added, and N, S heteroatoms are not doped in the pyrolysis process, so that the obtained carbon material has fewer defect sites, fewer active sites and low coulombic efficiency of the first circle, which is only 20%. In the electrochemical circulation process, the slurry prepared by mixing and grinding comparative example 2, carbon black and sodium carboxymethyl cellulose has poor adhesion on the surface of copper foil, is easy to fall off from the surface of the copper foil, causes poor contact, and has poor circulation stability, 1 A.g-1After 50 cycles under the current density, irreversible inactivation occurs.
The rate performance and long cycle performance of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 as a negative electrode of a potassium ion battery are shown in fig. 5 and 6. As can be seen from fig. 5, the nitrogen-oxygen-sulfur-doped carbon negative electrode material prepared in example 1 of the present invention has good rate capability and small current cycling stability, and after the rate cycling is completed, the current at a low current (the current density is 0.1A · g)-1) After the circulation is continued for 70 circles, the specific capacity is not obviously reduced. As can be seen from FIG. 6, the material has good long-cycle stability at a current density of 1 A.g-1After 1000 cycles of lower circulation (0.1A g)-1Three lower activation cycles), the specific capacity is not obviously reduced, and the capacity retention rate reaches 95 percent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The preparation method of the nitrogen-oxygen-sulfur doped carbon negative electrode material is characterized by comprising the following steps of:
uniformly mixing citrate and an organic compound containing N and S, carrying out heat treatment at 400-900 ℃ in an inert gas atmosphere, and cleaning to obtain the product;
the organic compound containing N and S is one or more of thiourea, melamine, dicyanodiamine or trithiocyanuric acid.
2. The method of claim 1, wherein the citrate is one or more of lithium citrate, potassium citrate, sodium citrate, potassium sodium citrate, ferric citrate, cupric citrate, magnesium citrate, ammonium citrate, and hydrates of the citrate.
3. The method according to claim 1, wherein the organic compound containing N and S is thiourea, melamine or dicyanodiamine.
4. The method according to claim 1, wherein the heat treatment is carried out at a temperature of 450 to 700 ℃.
5. The method according to claim 1, wherein the heat treatment is carried out for 30 to 360 min.
6. The method according to claim 1, wherein the mass ratio of the citrate to the N-and S-containing organic compound is 1 (0.05-2).
7. The method according to claim 1, wherein the mass ratio of the citrate to the N-and S-containing organic compound is 1 (0.1-2).
8. The method of claim 1, wherein the inert gas comprises nitrogen or argon.
9. A nitrogen-oxygen-sulfur doped carbon negative electrode material is characterized by being obtained by the preparation method of any one of claims 1 to 8.
10. The use of the nitrogen oxygen sulfur doped carbon negative electrode material of claim 9 in the preparation of a negative electrode material for a potassium ion battery.
CN202210023772.1A 2022-01-10 2022-01-10 Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof Pending CN114530598A (en)

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