CN115275151A - Vanadium disulfide/titanium carbide composite material and preparation method and application thereof - Google Patents

Vanadium disulfide/titanium carbide composite material and preparation method and application thereof Download PDF

Info

Publication number
CN115275151A
CN115275151A CN202210975945.XA CN202210975945A CN115275151A CN 115275151 A CN115275151 A CN 115275151A CN 202210975945 A CN202210975945 A CN 202210975945A CN 115275151 A CN115275151 A CN 115275151A
Authority
CN
China
Prior art keywords
composite material
vanadium
titanium carbide
vanadium disulfide
carbide composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210975945.XA
Other languages
Chinese (zh)
Inventor
王明珊
曾敏
李恩智
陈淋
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.)
Southwest Petroleum University
Original Assignee
Southwest Petroleum University
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 Southwest Petroleum University filed Critical Southwest Petroleum University
Priority to CN202210975945.XA priority Critical patent/CN115275151A/en
Publication of CN115275151A publication Critical patent/CN115275151A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides a vanadium disulfide/titanium carbide composite material and a preparation method and application thereof, belonging to the technical field of sodium ion battery electrode materials. In the invention, ti 3 AlC 2 Etching and ultrasonic stripping are sequentially carried out to obtain few-layer Ti 3 C 2 T x A dispersion liquid; mixing a vanadium source in an organic solvent to obtain a mixed solution; taking few Ti layers 3 C 2 T x Mixing the dispersion with ethanol, centrifuging, and mixingMixing the precipitate obtained by centrifugation with the mixed solution to obtain a suspension; mixing the suspension with a sulfur source, and then carrying out solvothermal reaction to obtain the vanadium disulfide/Ti 3 C 2 T x A composite material. According to the vanadium disulfide/titanium carbide composite material prepared by the invention, the vanadium disulfide nanosheets grow uniformly, large-scale agglomeration phenomenon is avoided, a good three-dimensional structure is formed with the titanium carbide framework, the volume effect of vanadium disulfide can be effectively relieved, and the rate capability of the material is enhanced.

Description

Vanadium disulfide/titanium carbide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion battery electrode materials, in particular to a vanadium disulfide/titanium carbide composite material and a preparation method and application thereof.
Background
Lithium ion batteries are the most popular electrochemical energy storage devices at present due to their advantages of high energy density, long service life and high operating voltage. However, the further development of lithium ion batteries is limited by the cost problem caused by insufficient abundance and uneven distribution of lithium resources and the safety problem caused by lithium dendrites. Sodium ion batteries have a similar operating principle as lithium ion batteries. In contrast, sodium resources are more abundant (2.3%) in the earth's crust than lithium resources, and the extraction cost is lower. The ductility of the metal sodium is higher than that of the metal lithium, so that dendrite with high mechanical strength is not easy to form, and the safety is higher. Meanwhile, sodium does not generate alloying reaction with aluminum, so that the copper foil can be used as a current collector of the cathode of the sodium-ion battery, and the cost of the sodium-ion battery is further reduced. These advantages make sodium ion batteries considered the most potential next generation electrochemical energy storage devices to replace lithium ion batteries.
However, the sodium ion battery has defects, because the radius of the sodium ion is larger than that of the lithium ion, so that the intercalation and deintercalation of the sodium ion need to overcome higher energy barrier, the requirement on electrode materials is higher, and many lithium ion battery negative electrode materials are not suitable for the sodium ion battery, especially the most classical graphite negative electrode materials. Therefore, the development of a novel sodium-ion battery negative electrode material has important application significance. The negative electrode materials currently studied mainly include carbon materials, alloying materials, metal oxides, metal chalcogenides, and the like. Among them, the carbon material shows a good cycle performance but has an unsatisfactory capacity, and the alloying material and the metal oxide/chalcogenide material have a high capacity but a large volume expansion during the cycle and a severe electrode pulverization, resulting in a rapid deterioration of the cycle stability. The contradiction between the electrode capacity and stability is a major problem faced by sodium ion batteries, and some measures are urgently needed to improve the contradiction.
Previous reports indicate that layered transition metal sulfides are excellent sodium ion host materials. The open two-dimensional structure and the generally larger interlayer distance of the sodium ion exchange membrane are beneficial to the rapid intercalation and deintercalation of sodium ions, and a sodium storage mechanism based on the conversion reaction can also provide enough energy density. Among them, vanadium-based sulfides (e.g. VS) 2 ) Is attractive by virtue of a series of advantages of the self-body. First is VS 2 The composite material has a typical two-dimensional layered structure, layers are connected through weak van der Waals force, the interlayer spacing is 0.575nm and is obviously larger than the radius (1.02 nm) of sodium ions, and therefore the composite material can have rich ion storage active sites and rapid sodium ion deintercalation kinetics. Second, the lower relative atomic mass and multi-valence states of vanadium cause VS 2 Has higher theoretical sodium storage capacity (932 mAh g) -1 ). Finally, the vanadium resource reserve in the crust is large (0.02%), china is a large vanadium resource country, and vanadium sulfide is considered as the sodium ion battery electrode material, so that the cost is low and the economic benefit is high. But VS 2 The method also has the common defects of metal sulfide materials, namely, the volume effect is large in the charging and discharging process, the electrode is pulverized and cracked seriously, and the rapid attenuation of the circulating capacity is caused. A commonly used solution for research involves VS 2 Carrying out carbon modification, nanocrystallization, shape regulation or introduction of a matrix material and the like.
The invention application with the publication number of CN111816858A discloses a preparation method and application of a sulfur/vanadium disulfide/MXene composite material, wherein the preparation process comprises the following steps: (1) Adding a vanadium salt solution and a sulfur source into the MXene suspension, and carrying out hydrothermal reaction to obtain a vanadium disulfide/MXene composite material; (2) And mixing and grinding the vanadium disulfide/MXene composite material and elemental sulfur to obtain a mixture, and then carrying out a melt diffusion reaction on the mixture to obtain the sulfur/vanadium disulfide/MXene composite material. Wherein the vanadium disulfide/MXene composite material is obtained by a hydrothermal method in the step (1). However, due to the sensitivity of the MXene material, the hydrothermal process can cause the oxidation of MXene, and meanwhile, the vanadium disulfide/MXene composite material obtained in the hydrothermal process has poor composite effect, and the vanadium disulfide with large size and the MXene cannot form a good three-dimensional nano structure, so that when the vanadium disulfide is applied to a battery, good electrode/electrolyte contact cannot be constructed.
Disclosure of Invention
The invention aims to provide a vanadium disulfide/titanium carbide composite material, and a preparation method and application thereof, and aims to solve the technical problems of large charge-discharge volume effect and too fast cycle capacity attenuation caused by taking a vanadium disulfide-based composite material as a negative electrode material of a sodium ion battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a vanadium disulfide/titanium carbide composite material, which comprises the following steps:
1) Mixing Ti 3 AlC 2 Etching and ultrasonic stripping are sequentially carried out to obtain few-layer Ti 3 C 2 T x Dispersion of Ti 3 C 2 T x Middle T x The group comprises one or more of-F, -OH and-COOH;
2) Mixing a vanadium source in an organic solvent to obtain a mixed solution;
3) Taking few Ti layers 3 C 2 T x Mixing the dispersion liquid with ethanol, then carrying out centrifugal treatment, and mixing the precipitate obtained by centrifugation with the mixed liquid to obtain a suspension;
4) Mixing the suspension with a sulfur source, and carrying out solvothermal reaction to obtain vanadium disulfide/Ti 3 C 2 T x A composite material;
wherein the step 1) and the step 2) are not in sequence.
Further, in the step 1), the etching agent used for etching is a hydrochloric acid-lithium fluoride mixed solvent, the concentration of hydrochloric acid in the hydrochloric acid-lithium fluoride mixed solvent is 8-10M, and the mass volume ratio of lithium fluoride to hydrochloric acid is 1g: 15-25 mL.
Further, in the step 1), ti 3 AlC 2 The mass volume ratio of the etching agent to the etching agent is 1g: 15-25 mL; the etching time is 20-28 h, and the etching temperature is 30-40 ℃; the frequency of the ultrasonic stripping is 20-100 KHz, and the time of the ultrasonic stripping is 1-2 h.
Further, in the step 2), the vanadium source comprises one or more of ammonium metavanadate, sodium metavanadate, vanadyl acetylacetonate and vanadyl sulfate, and the organic solvent comprises one or more of ethylene glycol, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the molar volume ratio of the vanadium source to the organic solvent is 1mmol:20 to 30mL.
Further, in the step 3), few Ti layers are formed 3 C 2 T x The volume ratio of the dispersion to the ethanol is 1:3 to 5;
vanadium source in the mixed solution and few layers of Ti in the suspension 3 C 2 T x The molar mass ratio of (1 mmol): 25-100 mg.
Further, in the step 3), the rotation speed of the centrifugal treatment is 5000-7000 rpm, and the time of the centrifugal treatment is 5-10 min.
Further, in the step 4), the sulfur source comprises one or more of thiourea, thioacetamide and cysteine, and the molar ratio of the vanadium source to the sulfur source in the suspension is 1:5 to 15.
Further, in the step 4), the temperature of the solvothermal reaction is 160-200 ℃, and the time of the solvothermal reaction is 16-24 h.
The invention provides a vanadium disulfide/titanium carbide composite material.
The invention provides an application of a vanadium disulfide/titanium carbide composite material in preparation of a sodium ion battery cathode, wherein the vanadium disulfide/titanium carbide composite material, a conductive agent and a binder are mixed according to a mass ratio of 5-7: 1 to 3: 1-3, coating the active slurry on a copper foil, and drying to obtain the sodium-ion battery cathode.
The invention has the beneficial effects that:
(1) The vanadium disulfide/Ti synthesized by the invention 3 C 2 T x Composite material, ti 3 C 2 T x A three-dimensional network structure is formed, and the vanadium disulfide nanosheet uniformly grows on Ti 3 C 2 T x In the three-dimensional framework, the three-dimensional structure effectively prevents the self-stacking of the vanadium disulfide nanosheets, and increases twoThe contact surface of vanadium sulfide and electrolyte increases the surface reaction chance of the material and shortens the diffusion path of sodium ions in the material.
(2)Ti 3 C 2 T x Enough expansion space is reserved for the composite material by forming a three-dimensional network structure, and electrode pulverization and cracking caused by the volume effect of vanadium disulfide can be effectively relieved, so that the circulation stability is improved, and meanwhile, the Ti with high conductivity is prepared 3 C 2 T x The conductivity of the vanadium disulfide can be improved, so that the composite material has excellent rate capability.
Drawings
FIG. 1 shows vanadium disulfide/Ti prepared in example 1 of the present invention 3 C 2 T x SEM images of the composite;
FIG. 2 shows the vanadium disulfide/Ti prepared in example 1 of the present invention 3 C 2 T x XRD pattern of the composite;
FIG. 3 shows vanadium disulfide/Ti prepared in comparative example 1 of the present invention 3 C 2 T x SEM images of the composite;
FIG. 4 shows vanadium disulfide/Ti in application example 1 of the present invention 3 C 2 T x The current density of the composite material is 10Ag -1 Time cycle stability profile;
FIG. 5 shows vanadium disulfide/Ti in application example 2 of the present invention 3 C 2 T x The current density of the composite material is 10Ag -1 Time cycle stability profile;
FIG. 6 shows vanadium disulfide/Ti in application example 3 of the present invention 3 C 2 T x The current density of the composite material is 1Ag -1 Graph of cycling stability over time.
Detailed Description
The invention provides a preparation method of a vanadium disulfide/titanium carbide composite material, which comprises the following steps:
1) Mixing Ti 3 AlC 2 Etching and ultrasonic stripping are sequentially carried out to obtain few-layer Ti 3 C 2 T x Dispersion, ti 3 C 2 T x Middle T x The radicals comprising in-F, -OH and-COOHOne or more of the components;
2) Mixing a vanadium source in an organic solvent to obtain a mixed solution;
3) Taking few Ti layers 3 C 2 T x Mixing the dispersion liquid with ethanol, then carrying out centrifugal treatment, and mixing the precipitate obtained by centrifugation with the mixed liquid to obtain a suspension;
4) Mixing the suspension with a sulfur source, and carrying out solvothermal reaction to obtain vanadium disulfide/Ti 3 C 2 T x A composite material;
wherein the step 1) and the step 2) are not in sequence.
In the present invention, T x The radical is preferably-F and/or-OH.
In the invention, in the step 1), the etchant used for etching is a hydrochloric acid-lithium fluoride mixed solvent, and the concentration of hydrochloric acid in the hydrochloric acid-lithium fluoride mixed solvent is 8-10M, preferably 9M.
In the invention, the mass volume ratio of lithium fluoride to hydrochloric acid in the hydrochloric acid-lithium fluoride mixed solvent is 1g:15 to 25mL, preferably 1g:18 to 22mL, more preferably 1g:20mL.
In the present invention, in said step 1), ti 3 AlC 2 The mass volume ratio of the etching agent to the etching agent is 1g:15 to 25mL, preferably 1g:18 to 22mL, more preferably 1g:20mL.
In the invention, in the step 1), the etching time is 20-28 h, and the etching temperature is 30-40 ℃; preferably, the etching time is 22-26 h, and the etching temperature is 32-38 ℃; further preferably, the etching time is 24h, and the etching temperature is 35 ℃.
In the invention, in the step 1), the frequency of ultrasonic stripping is 20-100 KHz, and the time of ultrasonic stripping is 1-2 h; preferably, the frequency of ultrasonic stripping is 40-70 KHz, and the time of ultrasonic stripping is 1-1.5 h; more preferably, the frequency of the ultrasonic stripping is 50-60 KHz, and the time of the ultrasonic stripping is 1.5h.
In the invention, the ultrasonic stripping is followed by the centrifugal treatment to obtain the few-layer Ti 3 C 2 T x Dispersion, said centrifugal treatmentThe rotating speed of the centrifugal machine is 3000-4000 rpm, and the time of centrifugal treatment is 0.5-2 h; preferably, the rotation speed of the centrifugation is 3500rpm, and the time of the centrifugation is 1 hour.
In the invention, in the step 2), the vanadium source comprises one or more of ammonium metavanadate, sodium metavanadate, vanadyl acetylacetonate and vanadyl sulfate, and preferably ammonium metavanadate and/or vanadyl acetylacetonate.
In the present invention, in the step 2), the organic solvent comprises one or more of ethylene glycol, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and is preferably ethylene glycol and/or N, N-dimethylformamide.
In the invention, in the step 2), the molar volume ratio of the vanadium source to the organic solvent is 1mmol:20 to 30mL, preferably 1mmol:22 to 28mL, more preferably 1mmol:25mL.
In the present invention, the temperature at which the vanadium source is mixed in the organic solvent is 30 to 60 ℃, preferably 40 to 50 ℃, and more preferably 45 ℃.
In the present invention, in the step 3), ti is less in thickness 3 C 2 T x The volume ratio of the dispersion liquid to the ethanol is 1:3 to 5, preferably 1:3.5 to 4.5, more preferably 1:4.
in the invention, the vanadium source in the mixed solution and the few-layer Ti in the suspension liquid 3 C 2 T x The molar mass ratio of (1 mmol): 25 to 100mg, preferably 1mmol:40 to 80mg, more preferably 1mmol:60mg.
In the invention, in the step 3), the rotation speed of the centrifugal treatment is 5000-7000 rpm, and the time of the centrifugal treatment is 5-10 min; preferably, the rotation speed of the centrifugal treatment is 5500-6500 rpm, and the time of the centrifugal treatment is 6-8 min; further preferably, the rotation speed of the centrifugal treatment is 6000rpm, and the time of the centrifugal treatment is 7min.
In the present invention, in the step 4), the sulfur source comprises one or more of thiourea, thioacetamide and cysteine, and is preferably thiourea and/or thioacetamide.
In the invention, in the step 4), the molar ratio of the vanadium source to the sulfur source in the suspension is 1:5 to 15, preferably 1:8 to 12, more preferably 1:10.
in the invention, in the step 4), the temperature of the solvothermal reaction is 160-200 ℃, and the time of the solvothermal reaction is 16-24 h; preferably, the temperature of the solvothermal reaction is 170-190 ℃, and the time of the solvothermal reaction is 18-22 h; further preferably, the temperature of the solvothermal reaction is 180 ℃ and the time of the solvothermal reaction is 20 hours.
The invention provides a vanadium disulfide/titanium carbide composite material.
The invention provides an application of a vanadium disulfide/titanium carbide composite material in preparation of a sodium ion battery cathode, wherein the vanadium disulfide/titanium carbide composite material, a conductive agent and a binder are mixed according to a mass ratio of (5-7): 1 to 3: 1-3, coating the active slurry on a copper foil, and drying to obtain the sodium-ion battery cathode.
In the invention, the ratio of the active slurry is preferably 6:2:2.
the technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Vanadium disulphide/titanium carbide (VS) 2 /Ti 3 C 2 T x ) Preparing a composite material:
1) 2g of lithium fluoride is dissolved in 40ml of 9M hydrochloric acid to prepare an etching agent, and then 2g of Ti is taken 3 AlC 2 Slowly adding into the etching agent, adding into the etching agent at 35 ℃, stirring and reacting for 24h. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of the supernatant is reached>6, pouring out the supernatant to obtain a plurality of layers of Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, bubbling at 500Hz, ultrasonic treating for 1h, centrifuging at 3500rpm/min for 1h, collecting the supernatant as Ti layer 3 C 2 T x And (3) dispersing the mixture.
2) 2mmol of ammonium metavanadate is heated to 50 ℃ and dissolved in 50ml of ethylene glycol with stirring to form a mixed solution.
3) Taking out the solution containing 100mg of Ti 3 C 2 T x Mass of less-layer Ti 3 C 2 T x Dispersion to which a small amount of Ti is added 3 C 2 T x And 3 times volume of ethanol of the dispersion liquid, shaking uniformly, centrifuging at 6000rpm/min for 10min at high speed, pouring off supernatant, mixing the residual precipitate and the obtained mixed solution, and performing ultrasonic treatment for 10min to obtain suspension.
4) Adding 20mmol of thioacetamide into the suspension, stirring for dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 180 ℃ for 20 hours, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally carrying out freeze drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti of this example 3 C 2 T x The phase of the composite material is characterized, and figure 1 shows vanadium disulfide/Ti 3 C 2 T x SEM image of the composite material shows that the composite material has good three-dimensional structure appearance, and vanadium disulfide and Ti 3 C 2 T x The uniform and stable three-dimensional porous structure is formed together, and the agglomeration phenomenon of the vanadium disulfide nanosheets does not occur. FIG. 2 shows vanadium disulfide/Ti 3 C 2 T x XRD pattern of the composite. The results show that the solvothermal preparation of VS 2 Good purity, each peak position is equal to VS of hexagonal system 2 The standard card (PDF # 89-1640) corresponds to the standard card, and no other obvious miscellaneous peaks appear. Introduction of Ti 3 C 2 T x Thereafter, the XRD pattern of the composite sample can be seen to be determined from Ti 3 C 2 T x Diffraction peak and VS of 2 The diffraction peaks of (A) together constitute a demonstration that the solvothermal method used in this example successfully constructed VS 2 With Ti 3 C 2 T x And is not to Ti 3 C 2 T x Oxidation occurs.
Example 2
Vanadium disulphide/titanium carbide (VS) 2 /Ti 3 C 2 T x ) Composite materialThe preparation of (1):
1) 2.4g of lithium fluoride is dissolved in 40ml of 9M hydrochloric acid to prepare an etching agent, and then 2g of Ti is taken 3 AlC 2 Slowly adding into the etching agent, adding into the etching agent at 40 ℃, stirring and reacting for 24h. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of the supernatant is reached>6, pouring out the supernatant to obtain a plurality of layers of Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, bubbling at 600Hz, ultrasonic treating for 1h, centrifuging at 3500rpm/min for 1h, collecting the supernatant as Ti layer 3 C 2 T x And (3) dispersing the mixture.
2) 2mmol of ammonium metavanadate is heated to 50 ℃ and dissolved in 50ml of ethylene glycol with stirring to form a mixed solution.
3) Taking out the solution containing 50mg of Ti 3 C 2 T x Mass of less Ti 3 C 2 T x A dispersion to which a small amount of Ti is added 3 C 2 T x 5 times volume of ethanol of the dispersion liquid, shaking up, centrifuging at 6000rpm/min for 10min, pouring off the supernatant, mixing the residual precipitate and the obtained mixed solution, and performing ultrasonic treatment for 10min to obtain a suspension.
4) Adding 20mmol of thiourea into the suspension, stirring for dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 180 ℃ for 16h, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally freeze-drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti obtained in example 2 3 C 2 T x The properties of the composite material were substantially identical to those of the composite material obtained in example 1.
Example 3
Vanadium disulphide/titanium carbide (VS) 2 /Ti 3 C 2 T x ) Preparing a composite material:
1) 2g of lithium fluoride is dissolved in 40ml of 9M hydrochloric acid to prepare an etching agent, and then 2g of Ti is taken 3 AlC 2 Slowly adding the mixture into the etching agent to form a mixture,stirring and reacting for 24h at 35 ℃. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of a supernatant>6, pouring out the supernatant to obtain a plurality of layers of Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, bubbling, ultrasonic treating at 400Hz for 1h, centrifuging at 4000rpm/min for 1h, and collecting the supernatant as Ti layer 3 C 2 T x And (3) dispersing the mixture.
2) 2mmol of vanadyl acetylacetonate are heated to 50 ℃ and dissolved in 50ml of N-methylpyrrolidone with stirring to form a mixture.
3) Taking out the solution containing 200mg of Ti 3 C 2 T x Mass of less Ti 3 C 2 T x Dispersion to which a small amount of Ti is added 3 C 2 T x And 3 times volume of ethanol of the dispersion liquid, shaking uniformly, centrifuging at 6000rpm/min for 10min at high speed, pouring off supernatant, mixing the residual precipitate and the obtained mixed solution, and performing ultrasonic treatment for 10min to obtain suspension.
4) Adding 10mmol of cysteine into the suspension, stirring and dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 200 ℃ for 24 hours, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally freeze-drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti obtained in example 3 3 C 2 T x The properties of the composite material were substantially identical to those of the composite material obtained in example 1.
Example 4
Vanadium disulphide/titanium carbide (VS) 2 /Ti 3 C 2 T x ) Preparing a composite material:
1) 2g of lithium fluoride was dissolved in 40ml of 10M hydrochloric acid to prepare an etchant, and 2g of Ti was subsequently added 3 AlC 2 Slowly adding into the etching agent, adding into the etching agent at 30 ℃, stirring and reacting for 24h. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of the supernatant is reached>6, pouring out the supernatant to obtainMultilayer Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, bubbling at 400Hz, ultrasonic treating for 2h, centrifuging at 4000rpm/min for 1h, and collecting the supernatant as Ti layer 3 C 2 T x And (3) dispersing the mixture.
2) 2mmol of vanadyl acetylacetonate are heated to 50 ℃ and dissolved in 50ml of N, N-dimethylformamide with stirring to form a mixture.
3) Taking out the solution containing 100mg of Ti 3 C 2 T x Mass of less Ti 3 C 2 T x Dispersion to which a small amount of Ti is added 3 C 2 T x And 3 times volume of ethanol of the dispersion liquid, shaking uniformly, centrifuging at 6000rpm/min for 10min at high speed, pouring off supernatant, mixing the residual precipitate and the obtained mixed solution, and performing ultrasonic treatment for 10min to obtain suspension.
4) Adding 20mmol thioacetamide into the suspension, stirring for dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 180 ℃ for 20 hours, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally freeze-drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti from example 4 3 C 2 T x The properties of the composite material were substantially identical to those of the composite material obtained in example 1.
Example 5
Vanadium disulphide/titanium carbide (VS) 2 /Ti 3 C 2 T x ) Preparing a composite material:
1) 2g of lithium fluoride is dissolved in 40ml of 8M hydrochloric acid to prepare an etching agent, and 2g of Ti is taken 3 AlC 2 Slowly adding into the etching agent, adding into the etching agent at 35 ℃, stirring and reacting for 24h. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of the supernatant is reached>6, pouring out the supernatant to obtain a plurality of layers of Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, and bubblingUltrasonic treating at 400Hz for 1h, centrifuging at 3500rpm/min for 1h, collecting the supernatant as Ti layer 3 C 2 T x And (3) dispersing the mixture.
2) 2mmol of ammonium metavanadate is heated to 40 ℃ and dissolved in 50ml of ethylene glycol under stirring to form a mixed solution.
3) Taking out the solution containing 200mg of Ti 3 C 2 T x Mass of less-layer Ti 3 C 2 T x Dispersion to which a small amount of Ti is added 3 C 2 T x And 3 times volume of ethanol of the dispersion liquid, shaking up, centrifuging at 6000rpm/min for 10min, pouring out supernatant, mixing the residual precipitate and the obtained mixed solution, and performing ultrasonic treatment for 10min to obtain suspension.
4) Adding 10mmol of thiourea into the suspension, stirring and dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 200 ℃ for 24 hours, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally freeze-drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti obtained in example 5 3 C 2 T x The properties of the composite material were substantially identical to those of the composite material obtained in example 1.
Comparative example 1
1) 2g of lithium fluoride is dissolved in 40ml of 9M hydrochloric acid to prepare an etching agent, and then 2g of Ti is taken 3 AlC 2 Slowly adding into the etching agent, adding into the etching agent at 35 ℃, stirring and reacting for 24h. After the reaction is finished, repeatedly centrifuging and washing the etching product by using deionized water at 3500rpm until the pH value of the supernatant is reached>6, pouring off the supernatant to obtain a multi-layer Ti 3 C 2 T x . Subsequent multi-layer of Ti 3 C 2 T x Dispersing in 100ml deionized water, introducing argon gas, bubbling at 500Hz, ultrasonic treating for 1h, centrifuging at 3500rpm/min for 1h, collecting the supernatant as Ti layer 3 C 2 T x Dispersing, then adding a small layer of Ti 3 C 2 T x Freeze drying the dispersion at-50 deg.C to obtain Ti with less layer 3 C 2 T x And (3) powder.
2) 2mmol of ammonium metavanadate is heated to 50 ℃ and dissolved in 50ml of ethylene glycol under stirring to form a mixed solution.
3) Taking a small layer of Ti containing 100mg of cold dry 3 C 2 T x Mixing the powder with the above mixed solution, and performing ultrasonic treatment for 30min to obtain suspension.
4) Adding 20mmol thioacetamide into the suspension, stirring for dissolving, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out solvothermal reaction at 180 ℃ for 20 hours, after the reaction is finished, waiting for the reaction kettle to be cooled to room temperature, centrifugally washing a black reaction product by using ethanol and deionized water, and finally freeze-drying to obtain vanadium disulfide/Ti 3 C 2 T x A composite material.
Vanadium disulfide/Ti obtained in comparative example 1 3 C 2 T x The phase of the composite material is characterized, and figure 3 shows vanadium disulfide/Ti 3 C 2 T x SEM image of composite material, it is obvious that few layers of Ti are used by cold drying 3 C 2 T x When the powder is used as a precursor, a large amount of vanadium disulfide nanosheets are agglomerated. But also a small part of vanadium disulfide nanosheets are grown on Ti 3 C 2 T x On the framework, the growth of the vanadium disulfide is not effectively regulated and the whole growth process is extremely uneven, which is probably similar to the few Ti layers after freeze-drying 3 C 2 T x Self-shrinkage of the powder, less Ti-layer after lyophilization 3 C 2 T x The specific surface area is reduced and effective nucleation growth sites cannot be provided. This comparative example demonstrates the use of ethanol centrifugation Ti as highlighted by the present invention 3 C 2 T x The key role of (1).
Application example 1
(1) The vanadium disulphide/Ti obtained in example 1 was used 3 C 2 T x The composite material, a conductive agent (acetylene black) and a binder (CMC + SBR) are prepared into active slurry according to the mass ratio of 6:2, then the active slurry is coated on copper foil, and the active slurry is dried in a vacuum oven for 24 hours and then used as a working electrode plate.
(2) Taking a metal sodium sheet as a counter electrode, and obtaining the electrode in the step (1)The sheet is a working electrode, 1MNaPF 6 Dissolving in ethylene glycol dimethyl ether as electrolyte, using glass fiber as a diaphragm, and assembling a CR2032 type button cell in an argon atmosphere glove box.
(3) Performing constant-current charge and discharge test on the button cell obtained in the step (2) at room temperature, wherein the voltage interval is 0.01-2.5V, performing cycle stability test on the cell, the cycle times are 100 times, and 0.1Ag is initially used -1 Circulating for 3 times, and subsequently testing the current density to be A.g -1 。
Fig. 4 is a graph showing the cycle stability of the electrode in application example 1. Composite electrode in A.g -1 Exhibits 738 mAh.g at a large current density -1 The initial discharge specific capacity of the lead-acid battery can still maintain 597mAh g after being cycled for 100 times -1 The high discharge specific capacity and the capacity retention rate of 80.9 percent indicate the good cycling stability of the material.
Application example 2
(1) The vanadium disulfide/Ti prepared in example 2 was used 3 C 2 T x The composite material, a conductive agent (acetylene black) and a binder (CMC + SBR) are prepared into active slurry according to the mass ratio of 6:2, then the active slurry is coated on copper foil, and the active slurry is dried in a vacuum oven for 24 hours and then used as a working electrode plate.
(2) Taking a metal sodium sheet as a counter electrode, taking the electrode sheet obtained in the step (1) as a working electrode, and taking 1MNaPF 6 Dissolving in ethylene glycol dimethyl ether as electrolyte, using glass fiber as a diaphragm, and assembling a CR2032 type button cell in an argon atmosphere glove box.
(3) And (3) carrying out constant current charge and discharge test on the button cell obtained in the step (2) at room temperature, wherein the voltage interval is 0.01-2.5V. The battery is subjected to a cycle stability test, the cycle frequency is 100 times, and 0.1Ag is initially used -1 Circulating for 3 times, and subsequently testing the current density to be A.g -1 。
Fig. 5 is a graph showing the cycle stability of the electrode in application example 2. Composite electrode in A.g -1 Exhibits 865 mAh.g at a high current density -1 The initial discharge specific capacity of the material still maintains 686mAh g after being cycled for 100 times -1 Has a high specific discharge capacity and a capacity retention ratio of79.3%, indicating good cycling stability of the material.
Application example 3
(1) The vanadium disulphide/Ti obtained in example 3 was used 3 C 2 T x The composite material, a conductive agent (acetylene black) and a binder (CMC + SBR) are prepared into active slurry according to the mass ratio of 6:2, then the active slurry is coated on copper foil, and the active slurry is dried in a vacuum oven for 24 hours and then used as a working electrode plate.
(2) Taking a metal sodium sheet as a counter electrode, taking the electrode sheet obtained in the step (1) as a working electrode, and taking 1M NaClO 4 The CR2032 type button cell was assembled in an argon atmosphere glove box by dissolving PC/DMC (5% fec addition) as an electrolyte and glass fiber as a separator.
(3) And (3) carrying out constant current charge and discharge test on the button cell obtained in the step (2) at room temperature, wherein the voltage interval is 0.01-2.5V. The battery is subjected to a cycle stability test, the cycle frequency is 100 times, and 0.1Ag is initially used -1 Circulating for 3 times, and measuring the current density of 1 A.g -1 。
Fig. 6 is a graph showing the cycle stability of the electrode in application example 3. In the ester electrolyte, the composite electrode is 1Ag -1 678 mAh.g is shown -1 The initial stable specific discharge capacity of the electrode is 294mAh g -1 After 100 times of circulation, 252mAh g is still maintained -1 Compared with the initial stable specific discharge capacity, the capacity retention rate of the lithium secondary battery is 85.6 percent. Although the capacity of the composite material in the ester electrolyte is lower than that of the ether electrolyte, the material still shows good cycling stability.
From the above embodiments, the invention provides a vanadium disulfide/titanium carbide composite material, and a preparation method and an application thereof. The vanadium disulfide/Ti prepared by the preparation method of the invention 3 C 2 T x The composite material has the advantages that the vanadium disulfide nanosheets grow uniformly, large-scale agglomeration phenomenon does not exist, a good three-dimensional structure is formed with the titanium carbide framework, the volume effect of vanadium disulfide can be effectively relieved, and the rate capability of the material is enhanced. The vanadium disulfide/Ti prepared by the invention 3 C 2 T x The composite material is prepared into a sodium ion battery cathode, the obtained battery has high initial discharge specific capacity, still has high discharge specific capacity after 100 cycles, and the capacity retention rate is as high as 85.6%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A preparation method of a vanadium disulfide/titanium carbide composite material is characterized by comprising the following steps:
1) Mixing Ti 3 AlC 2 Etching and ultrasonic stripping are sequentially carried out to obtain few-layer Ti 3 C 2 T x Dispersion of Ti 3 C 2 T x Middle T x The group comprises one or more of-F, -OH and-COOH;
2) Mixing a vanadium source in an organic solvent to obtain a mixed solution;
3) Taking few Ti layers 3 C 2 T x Mixing the dispersion liquid with ethanol, then carrying out centrifugal treatment, and mixing the precipitate obtained by centrifugation with the mixed liquid to obtain a suspension;
4) Mixing the suspension with a sulfur source, and then carrying out solvothermal reaction to obtain the vanadium disulfide/Ti 3 C 2 T x A composite material;
wherein the step 1) and the step 2) are not in sequence.
2. The method for preparing the vanadium disulfide/titanium carbide composite material according to claim 1, wherein in the step 1), the etching agent used for etching is a hydrochloric acid-lithium fluoride mixed solvent, the concentration of hydrochloric acid in the hydrochloric acid-lithium fluoride mixed solvent is 8-10M, and the mass volume ratio of lithium fluoride to hydrochloric acid is 1g: 15-25 mL.
3. The method of preparing a vanadium disulfide/titanium carbide composite material according to claim 2, wherein said step1) In (Ti) 3 AlC 2 The mass volume ratio of the etching agent to the etching agent is 1g: 15-25 mL; the etching time is 20-28 h, and the etching temperature is 30-40 ℃; the frequency of the ultrasonic stripping is 20-100 KHz, and the time of the ultrasonic stripping is 1-2 h.
4. The method for preparing the vanadium disulfide/titanium carbide composite material according to any one of claims 1 to 3, wherein in the step 2), the vanadium source comprises one or more of ammonium metavanadate, sodium metavanadate, vanadyl acetylacetonate and vanadyl sulfate, and the organic solvent comprises one or more of ethylene glycol, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the molar volume ratio of the vanadium source to the organic solvent is 1mmol:20 to 30mL.
5. The method for preparing the vanadium disulfide/titanium carbide composite material according to claim 4, wherein in the step 3), few Ti layers are formed 3 C 2 T x The volume ratio of the dispersion liquid to the ethanol is 1:3 to 5;
vanadium source in the mixed solution and few layers of Ti in the suspension 3 C 2 T x The molar mass ratio of (a) to (b) is 1mmol: 25-100 mg.
6. The method for preparing the vanadium disulfide/titanium carbide composite material according to claim 1, 2, 3 or 5, wherein in the step 3), the rotation speed of the centrifugal treatment is 5000-7000 rpm, and the time of the centrifugal treatment is 5-10 min.
7. The method for preparing the vanadium disulfide/titanium carbide composite material according to claim 6, wherein in the step 4), the sulfur source comprises one or more of thiourea, thioacetamide and cysteine, and the molar ratio of the vanadium source to the sulfur source in the suspension is 1:5 to 15.
8. The preparation method of the vanadium disulfide/titanium carbide composite material according to claim 5 or 7, wherein in the step 4), the temperature of the solvothermal reaction is 160-200 ℃, and the time of the solvothermal reaction is 16-24 h.
9. A vanadium disulphide/titanium carbide composite material obtainable by the method of manufacturing a vanadium disulphide/titanium carbide composite material according to any one of claims 1 to 8.
10. The application of the vanadium disulfide/titanium carbide composite material in the preparation of a negative electrode of a sodium-ion battery, which is characterized in that the vanadium disulfide/titanium carbide composite material obtained in the claim 9, a conductive agent and a binder are mixed in a mass ratio of (5-7): 1 to 3: 1-3, coating the active slurry on a copper foil, and drying to obtain the sodium-ion battery cathode.
CN202210975945.XA 2022-08-15 2022-08-15 Vanadium disulfide/titanium carbide composite material and preparation method and application thereof Pending CN115275151A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210975945.XA CN115275151A (en) 2022-08-15 2022-08-15 Vanadium disulfide/titanium carbide composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210975945.XA CN115275151A (en) 2022-08-15 2022-08-15 Vanadium disulfide/titanium carbide composite material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115275151A true CN115275151A (en) 2022-11-01

Family

ID=83750122

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210975945.XA Pending CN115275151A (en) 2022-08-15 2022-08-15 Vanadium disulfide/titanium carbide composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115275151A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117317197A (en) * 2023-11-16 2023-12-29 湖南娄底华星锑业有限公司 Negative electrode material of antimony-based sodium ion battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117317197A (en) * 2023-11-16 2023-12-29 湖南娄底华星锑业有限公司 Negative electrode material of antimony-based sodium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN105810914A (en) Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material
CN112018344B (en) Carbon-coated nickel sulfide electrode material and preparation method and application thereof
US20140255787A1 (en) Active material for batteries
Piana et al. A new promising sol–gel synthesis of phospho-olivines as environmentally friendly cathode materials for Li-ion cells
CN110783568B (en) Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure
CN107732203B (en) Preparation method of nano cerium dioxide/graphene/sulfur composite material
CN107394178B (en) Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof
CN114864896A (en) In-situ carbon-coated nano lithium iron phosphate cathode material and preparation method thereof
CN108899499B (en) Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery
CN114744152A (en) Vanadium tetrasulfide/vanadium carbide composite material and preparation method and application thereof
CN109279663B (en) Borate sodium-ion battery negative electrode material and preparation and application thereof
CN114094078A (en) Nitrogen-doped carbon-coated metal sulfide heterojunction material, preparation method and battery application
CN115275151A (en) Vanadium disulfide/titanium carbide composite material and preparation method and application thereof
CN113772718A (en) SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN112670669A (en) Nitrogen-doped carbon-coated Co and/or Co3Application of ZnC composite material in preparation of lithium-sulfur battery diaphragm
CN114613969A (en) Molybdenum-based core-shell structure material and preparation method and application thereof
WO2018195837A1 (en) Metal-sulfur battery and preparation method therefor
CN113968590A (en) Alkali metal ion intercalation SnS2Preparation method thereof, application of preparation method in battery negative electrode material and preparation method
CN114084882A (en) Doping of different valence states with Na3V2(PO4)2F3Carbon-coated cubic crystal material and preparation method and application thereof
CN113991103A (en) Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material
CN107394177B (en) Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof
CN111403725A (en) Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof
CN113725434B (en) Nickel-based metal organic frame derived composite electrode and preparation method thereof
CN114242982B (en) Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination