CN112968173A - Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material - Google Patents

Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material Download PDF

Info

Publication number
CN112968173A
CN112968173A CN202110134898.1A CN202110134898A CN112968173A CN 112968173 A CN112968173 A CN 112968173A CN 202110134898 A CN202110134898 A CN 202110134898A CN 112968173 A CN112968173 A CN 112968173A
Authority
CN
China
Prior art keywords
manganese
porous carbon
electrode material
composite electrode
organic framework
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
CN202110134898.1A
Other languages
Chinese (zh)
Inventor
张孝杰
周寿斌
王帅
吴战宇
黄毅
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.)
Jiangsu Huafu Storage New Technology Development Co ltd
Original Assignee
Jiangsu Huafu Storage New Technology Development Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Huafu Storage New Technology Development Co ltd filed Critical Jiangsu Huafu Storage New Technology Development Co ltd
Priority to CN202110134898.1A priority Critical patent/CN112968173A/en
Publication of CN112968173A publication Critical patent/CN112968173A/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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a porous carbon-coated sulfur vacancy composite electrode material, a preparation method thereof and a circular electrode using the material, which comprises the following steps that 1, inorganic manganese salt and terephthalic acid or 1, 3, 5-benzene tricarboxylic acid are mixed according to the molar ratio of 1: (0.8-5) respectively dissolving in a solvent to obtain an inorganic manganese salt solution and a terephthalic acid solution or a 1, 3, 5-benzene tricarboxylic acid solution; 2, uniformly mixing the solutions, and then standing and growing for 8-50 hours at 50-100 ℃ to obtain an initial product of the manganese-based metal organic framework template; 3, centrifugally separating the primary product, and washing the product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template; 4, mixing the organic framework template obtained in the step 3 with a sulfur source in a mass ratio of 1: (1-5) after mixing, raising the temperature to 900 ℃ at a rate of 2-10 ℃/min, and maintaining the temperature for 2-8 hours for pyrolysis reaction; 5 after the reaction is finished, cooling to room temperature. The composite electrode material prepared by the invention has high specific capacity and good cycling stability.

Description

Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material
Technical Field
The invention relates to a porous carbon-coated sulfur vacancy composite electrode material, a preparation method of the porous carbon-coated sulfur vacancy composite electrode material, a circular electrode adopting the porous carbon-coated sulfur vacancy composite electrode material, and belongs to the technical field of negative electrode materials of sodium-ion batteries.
Background
With the increasing demand for energy in human society, the problems of energy shortage and environmental pollution are attracting more and more extensive attention. The development and utilization of clean energy such as wind energy, solar energy, geothermal energy and the like are imperative, however, the discontinuity of time and space exists in the energy, and an effective way for realizing the sustainable development of the clean energy is to design and develop efficient energy storage equipment. Since the commercialization of lithium ion batteries in the early 90 s of the 20 th century, lithium ion batteries have been widely used in various fields, and the energy storage device has greatly assisted the storage and utilization of clean energy. The increasing demand for lithium ion batteries, and the limitation of uneven distribution and limited reserves of lithium resources, the cost of lithium ion batteries is rapidly increasing, and therefore, an energy storage device based on abundant resources needs to be found to partially replace the lithium ion batteries.
The sodium ion battery is a potential choice for a new generation of large-scale energy storage technology due to abundant sodium resource reserves and relatively low raw material cost. Although sodium ions are physically and chemically similar to lithium ions, there are great differences in some aspects such as a higher standard electrode potential of sodium, a larger radius of sodium ions, etc., and thus, there is an urgent need to develop an advanced electrode material having a high specific capacity and rapid sodium ion transport kinetics. Transition metal chalcogenides are widely used in sodium ion batteries due to their open framework structure and good electrochemical performance. As a typical metal sulfide, MnS has a plurality of advantages of large interlayer spacing and the like, so that when the MnS is used as a negative electrode material of a sodium-ion battery, rapid sodium ion transmission can be realized. However, the low conductivity and large volume expansion effect lead to poor specific capacity, rate capability and cycle life.
The Chinese patent with publication number CN 106159239B discloses a preparation method of a manganese sulfide/graphene nano composite material, which comprises the following steps: A. a hydrothermal process: dispersing graphite oxide in water, performing ultrasonic treatment to obtain a graphene oxide solution, adding sulfuric acid into the solution, performing ultrasonic dispersion uniformly to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting at 160-260 ℃ for 18-30 hours, taking out and washing to obtain three-dimensional columnar reduced graphene oxide; B. a compounding procedure: dissolving manganese salt and a sulfur source in an organic solvent to prepare a mixed solution, then putting the three-dimensional columnar reduced graphene oxide into the solution, and soaking for more than 1 day at the temperature of 3-50 ℃; and finally, transferring the mixed solution and the three-dimensional columnar reduced graphene oxide into a hydrothermal reaction kettle, reacting for 18-30 hours at 160-240 ℃, and washing and drying the product to obtain the manganese sulfide/graphene nanocomposite.
The Chinese patent application with the publication number of CN 108011099A discloses a preparation method of a manganese sulfide/carbon nano tube composite material, which comprises the following steps: (1) preparing mixed acid from concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1:3, adding carbon nano tubes with the tube diameters of 10-40 nm, placing the mixed acid in a water bath at the temperature of 50-80 ℃, stirring for 4-8 hours, removing acid liquor, and then cleaning the mixed acid with distilled water in a repeated centrifugation and suction filtration mode until the pH value of the washed filtrate is 6-7; (2) adding the carbon nano tube obtained in the step (1) and a surfactant into a solvent, carrying out ultrasonic treatment for 0.5-1 h to form a uniform suspension, then adding a sulfur source and manganese salt, and carrying out ultrasonic treatment for 1-2 h, wherein the carbon nano tube: surfactant (b): a sulfur source: manganese salt: the mass ratio of the solvent is 1: 1-1.5: 20-30: 15-30: 500; (3) pouring the mixed solution obtained in the step (2) into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven at the temperature of 150-200 ℃, reacting for 12-24 hours to obtain a black substance, then alternately washing the black substance with ethanol and deionized water for a plurality of times, and carrying out vacuum drying or freeze drying on the product at the temperature of 40-60 ℃ to obtain the black manganese sulfide/carbon nanotube composite material.
The Chinese patent with the publication number of CN 108394937B discloses a preparation method of a manganese iron sulfide solid solution, wherein a Prussian blue-like coordination compound manganese hexacyanoferrate is used as a precursor, and the manganese iron sulfide solid solution is obtained by vulcanization under the protection of inert gas; the method comprises the following steps: mixing the components in percentage by weight: grinding and uniformly mixing the precursor manganese hexacyanoferrate and excessive sulfur powder to obtain a mixture; n calcination: placing the mixture in a sealed tube furnace, and calcining under the protection of inert gas to obtain a manganese iron sulfide solid solution; the calcining step is specifically as follows: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, wherein in the heating process, the temperature is increased from room temperature to 250-280 ℃ at the heating rate of 5-7 ℃/min, the temperature is maintained at 250-280 ℃ for calcining for 1-2 hours, then the temperature is increased from 250-280 ℃ to 550-600 ℃ at the heating rate of 3-5 ℃/min, the temperature is maintained at 550-600 ℃ for calcining for 6-7 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
The above techniques are aimed at improving the conductivity of the electrode material, i.e. enhancing the sodium ion transport kinetics, but still focus on morphology control and modification of the electrode material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a porous carbon-coated sulfur vacancy composite electrode material which is high in specific capacity and good in cycling stability.
In order to solve the technical problems, the technical scheme of the invention is to provide a porous carbon-coated sulfur vacancy composite electrode material, wherein sulfur vacancies exist in porous carbon-coated manganese sulfide particles in the composite electrode material, the particle size of the porous carbon-coated manganese sulfide particles is 10-50 nanometers, and the porous carbon-coated manganese sulfide composite material is prepared by heat treatment of a metal organic framework.
The invention has the beneficial effects that: when the porous carbon-coated sulfur vacancy composite electrode material is used as a sodium ion battery cathode material, the porous carbon-coated sulfur vacancy composite electrode material has the advantages of rapid sodium ion transmission, high specific capacity, excellent cycle performance and rate capability and the like.
The invention also aims to solve the problems in the prior art and provide the preparation method of the porous carbon-coated sulfur vacancy composite electrode material, which has the advantages of high specific capacity, good cycling stability, simple preparation method, no pollution, low cost and the like.
In order to solve the technical problems, the technical scheme of the invention is to provide a preparation method of a porous carbon-coated sulfur vacancy composite electrode material, which sequentially comprises the following steps,
step 1: mixing inorganic manganese salt and terephthalic acid or 1, 3, 5-benzene tricarboxylic acid according to a molar ratio of 1: (0.8-5) respectively dissolving in a solvent to obtain an inorganic manganese salt solution and a terephthalic acid solution or a 1, 3, 5-benzene tricarboxylic acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing an inorganic manganese salt solution and a terephthalic acid solution or a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 8-50 hours at 50-100 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with a sulfur source in a mass ratio of 1: (1-5) after mixing, under the protection of high-purity argon, raising the temperature to 900 ℃ at the temperature-raising rate of 2-10 ℃/min, and keeping the temperature for 2-8 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Further, the inorganic manganese salt is manganese chloride, manganese acetate, manganese nitrate or manganese sulfate, and the sulfur source is thiourea or sublimed sulfur.
Further, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid in the step 1 is 1: 0.8.
Further, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid in the step 1 is 1: 3.
Further, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid in the step 1 is 1: 5.
Further, the temperature in the step 2 is 100 ℃, and the standing growth time is 8 hours.
Further, in the step 4, the manganese-based metal organic framework template and thiourea are mixed according to the mass ratio of 1:4, the heating rate is 2-10 ℃/min, the temperature is increased to 600 ℃, and the pyrolysis reaction time is 6 hours.
Further, in the step 4, the manganese-based metal organic framework template and the sublimed sulfur are mixed according to the mass ratio of 1:5, the heating rate is 3 ℃/min, the temperature is increased to 900 ℃, and the pyrolysis reaction time is 2 hours.
The invention achieves the following beneficial effects: (1) in the pyrolysis process of the manganese-based metal organic framework template, due to the decomposition of organic ligands into small molecule gases such as CO, CO2, NH3, H2O and the like, a multi-pore structure is formed in the electrode material, and the structure can effectively promote the gap diffusion of sodium ions in the electrode material.
The sodium ion transmission rate in the manganese sulfide electrode material can be greatly improved by constructing a proper amount of sulfur vacancies in the crystal structure of the porous carbon-coated sulfur vacancy composite electrode material to provide efficient vacancy diffusion.
And a porous conductive network is formed, so that the conductivity of the electrode material is improved, and the charge transfer resistance is reduced.
The volume expansion effect of sodium ions in the process of deintercalation of the electrode material is relieved, so that the porous carbon-coated sulfur vacancy composite electrode material obtained based on the method can show good electrochemical performance when being used as a sodium ion battery cathode material.
There are two forms of ion transport in the electrode material: interstitial diffusion and vacancy diffusion. The rapid transmission of sodium ions can be realized only by optimizing and regulating two forms of ion transmission, and the performance of the sodium ion battery can be comprehensively improved. The invention utilizes the metal organic framework to regulate and control the gap diffusion and vacancy diffusion of the manganese sulfide electrode material, and improves the transmission dynamics of sodium ions in the manganese sulfide electrode material. The metal organic framework is used as a crystal material formed by self-assembly of metal ions and organic ligands, and has the advantages of high porosity, large specific surface area, adjustable structure and function and the like, so that the metal organic framework becomes an energy storage material with great development potential.
The preparation method is simple, low in cost and easy to realize industrial large-scale application.
The manganese-based metal organic framework template prepared by the invention is of a rod-shaped structure, the surface is smooth, the size and length are 5 mu m, and the diameter is 50-500 nm.
From a transmission electron microscope image of the porous carbon-coated sulfur vacancy composite material prepared by the invention, it can be seen that the surface becomes rough and a porous structure is obviously seen after heat treatment, the rod-like structure of a parent material is well maintained, and the particle size of internal manganese sulfide can be seen to be 10-50 nm.
A circular electrode manufactured by adopting the porous carbon-coated sulfur vacancy composite electrode material is assembled into a CR2025 button cell in a glove box with water and oxygen contents of less than 0.5ppm by taking a metal sodium sheet as a reference electrode and a counter electrode and Whatman GF/D as a diaphragm. The electrolyte component is a mixed solvent (mass ratio of 1:1: 1) of 1M NaClO4 dissolved in ethylene carbonate, diethyl carbonate and ethyl methyl carbonate. The CR2025 button cell is charged and discharged at constant current (0.005-3.0V) by a blue cell tester CT2001A, the current density is 100mA/g, and the sodium storage capacity is up to 256-298 mAh/g; after 200 times of cyclic charge and discharge, the capacity retention rate is higher than 96.8%.
The porous carbon-coated sulfur vacancy composite electrode material has the sodium ion battery cycle performance under the current density of 100mA/g, the sodium storage capacity after 100 times is 282 mAh/g, and the cycle stability is better.
The porous carbon-coated sulfur vacancy composite electrode material still has a sodium storage capacity of 125 mAh/g under the condition of a large current density of 10A/g, and when the current density is reduced to 0.1A/g from 10A/g again, the reversible capacity is recovered to 280mAh/g, which indicates that the porous carbon-coated sulfur vacancy composite electrode material has better rate performance.
The invention further aims to solve the problems in the prior art and provide a circular electrode prepared from the porous carbon-coated sulfur vacancy composite electrode material, which has high sodium storage capacity and high capacity retention rate after repeated cyclic charge and discharge.
In order to solve the technical problems, the technical scheme of the invention is to provide a circular electrode prepared from a porous carbon-coated sulfur vacancy composite electrode material, and the preparation method comprises the following steps: dispersing the porous carbon-coated sulfur vacancy composite electrode material prepared according to the claims 2 to 9, a binder sodium carboxymethyl cellulose and a conductive agent Super-P in deionized water to prepare slurry, wherein the mass ratio of the raw materials is as follows: binder sodium carboxymethylcellulose: conducting agent Super-P = 75: 15: 10, uniformly coating the slurry on a copper foil with the thickness of 9 μm, drying in vacuum for 12 hours, and cutting to obtain a circular electrode with the diameter of 14 mm.
The beneficial effects obtained by the invention are as above, and are not described in detail.
Drawings
FIG. 1 is a scanning electron micrograph of a manganese-based metal organic framework template prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the porous carbon-coated sulfur vacancy composite electrode material prepared in example 1 of the present invention;
FIG. 3 is a graph of the cycle performance of a sodium ion battery of the composite material prepared in example 1 of the present invention;
fig. 4 is a graph of the rate performance of a sodium ion battery of the composite material prepared in example 11 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example 1
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese acetate and 1, 3, 5-benzene tricarboxylic acid are mixed according to a molar ratio of 1:1 are respectively dissolved in a solvent to obtain a manganese acetate solution and a 1, 3, 5-benzene trimethyl acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese acetate solution and a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 10 hours at 50 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template; as shown in FIG. 1, the manganese-based metal organic framework template prepared in example 1 has a rod-like structure, a smooth surface, a dimension of 5 μm in length and a diameter of 50-500 nm.
And 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with sublimed sulfur according to the mass ratio of 1: 2, under the protection of high-purity argon, raising the temperature to 300 ℃ at a temperature rise rate of 2 ℃/min, and keeping the temperature for 6 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
FIG. 2 is a transmission electron microscope image of the prepared porous carbon-coated sulfur vacancy composite material, and it can be seen that the surface becomes rough and a porous structure is clearly seen after heat treatment, the rod-like structure of the matrix material is well maintained, and it can be seen that the particle size of the internal manganese sulfide is 10-50 nm.
Example 2
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese chloride and terephthalic acid are mixed according to a molar ratio of 1:0.8, respectively dissolving in a solvent to obtain a manganese chloride solution and a terephthalic acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese chloride solution and a terephthalic acid solution in a dropwise manner, and then standing and growing for 24 hours at 80 ℃ to obtain an initial product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with sublimed sulfur according to the mass ratio of 1:4, under the protection of high-purity argon, raising the temperature to 600 ℃ at a temperature rise rate of 5 ℃/min, and keeping the temperature for 8 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 3
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese nitrate and 1, 3, 5-benzene tricarboxylic acid are mixed according to a molar ratio of 1:3, respectively dissolving in a solvent to obtain a manganese nitrate solution and a 1, 3, 5-benzene trimethyl acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese nitrate solution and a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 50 hours at 80 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with thiourea in a mass ratio of 1:5, after mixing, under the protection of high-purity argon, raising the temperature to 800 ℃ at a temperature rise rate of 7 ℃/min, and keeping the temperature for 10 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 4
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese nitrate and terephthalic acid are mixed according to a molar ratio of 1:5, respectively dissolving the manganese nitrate solution and the terephthalic acid solution in a solvent to obtain a manganese nitrate solution and a terephthalic acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese nitrate solution and a terephthalic acid solution in a dropwise manner, and then standing and growing for 12 hours at 100 ℃ to obtain an initial product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with sublimed sulfur according to the mass ratio of 1:5, after mixing, under the protection of high-purity argon, raising the temperature to 900 ℃ at the temperature rise rate of 3 ℃/min, and keeping the temperature for 2 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 5
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese chloride and 1, 3, 5-benzene tricarboxylic acid are mixed according to a molar ratio of 1:3, respectively dissolving the manganese chloride solution and the terephthalic acid solution or the 1, 3, 5-benzene trimethyl acid solution in a solvent, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese chloride solution and a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 8 hours at 100 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with thiourea in a mass ratio of 1:4, under the protection of high-purity argon, raising the temperature to 600 ℃ at a temperature rise rate of 10 ℃/min, and keeping the temperature for 6 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 6
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese chloride and terephthalic acid are mixed according to a molar ratio of 1: 2, respectively dissolving the manganese chloride solution and the terephthalic acid solution in a solvent to obtain a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese chloride solution and a terephthalic acid solution in a dropwise manner, and then standing and growing for 20 hours at 60 ℃ to obtain an initial product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with sublimed sulfur according to the mass ratio of 1:1, under the protection of high-purity argon, raising the temperature to 700 ℃ at a temperature rise rate of 7 ℃/min, and keeping the temperature for 8 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 7
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese acetate and terephthalic acid are mixed according to a molar ratio of 1:4, respectively dissolving the manganese acetate solution and the terephthalic acid solution in a solvent to obtain a manganese acetate solution and a terephthalic acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese acetate solution and a terephthalic acid solution in a dropwise manner, and then standing and growing for 10 hours at 50 ℃ to obtain an initial product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with sublimed sulfur according to the mass ratio of 1: 2, under the protection of high-purity argon, raising the temperature to 800 ℃ at a temperature rise rate of 10 ℃/min, and keeping the temperature for 2 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 8
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese sulfate and terephthalic acid are mixed according to a molar ratio of 1:3, respectively dissolving the manganese sulfate solution and the terephthalic acid solution in a solvent to obtain a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese sulfate solution and a terephthalic acid solution in a dropwise manner, and then standing and growing for 24 hours at 50 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with thiourea in a mass ratio of 1: 2, under the protection of high-purity argon, raising the temperature to 800 ℃ at a temperature rise rate of 8 ℃/min, and keeping the temperature for 4 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 9
The preparation method of the porous carbon-coated sulfur vacancy composite electrode material sequentially comprises the following steps of:
step 1: manganese nitrate and 1, 3, 5-benzene tricarboxylic acid are mixed according to a molar ratio of 1:4, respectively dissolving in a solvent to obtain a manganese nitrate solution and a 1, 3, 5-benzene trimethyl acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing a manganese nitrate solution and a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 20 hours at 100 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with thiourea in a mass ratio of 1:4, under the protection of high-purity argon, raising the temperature to 700 ℃ at a temperature rise rate of 6 ℃/min, and keeping the temperature for 5 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
Example 10
The porous carbon-coated sulfur vacancy composite electrode material prepared in examples 1 to 9, the binder carboxymethylcellulose sodium and the conductive agent Super-P were dispersed in deionized water at a mass ratio of 75: 15: 10 to prepare a slurry, which was uniformly coated on a copper foil 9 μm thick, and vacuum-dried for 12 hours to prepare a circular electrode 14mm in diameter.
A metal sodium sheet is used as a reference electrode and a counter electrode, Whatman GF/D is used as a diaphragm, and the CR2025 button cell is assembled in a glove box with the water and oxygen contents of less than 0.5 ppm. The electrolyte component is a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in which 1M NaClO4 is dissolved in a mass ratio of 1:1: 1. The CR2025 button cell is subjected to constant-current charging and discharging through a blue battery tester CT2001A, the voltage value is 0.005-3V, the current density is 100mA/g, the cycle performance of the porous carbon-coated sulfur vacancy composite electrode material is tested for 200 times of charging and discharging, and the electrochemical performance results of each electrode are shown in Table 1.
TABLE 1
Figure 454DEST_PATH_IMAGE002
Example 11
The composite electrode material of example 6 was assembled into a sodium ion battery as in example 10, and the assembled battery was cycled for 10 cycles at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0A/g, and then returned to 0.1A/g for rate capability testing.
The sodium ion battery was cycled 100 times at a current density of 100mA/g using the CR2025 button cell assembled in example 1. The obtained result is shown in fig. 3, the porous carbon-coated sulfur vacancy composite electrode material prepared in example 1 has a sodium ion battery cycle performance under a current density of 100mA/g, a sodium storage capacity of 282 mAh/g after 100 times, and has good cycle stability.
As shown in fig. 4, the porous carbon-coated sulfur vacancy composite electrode material prepared in example 11 has sodium ion battery rate performance at different current densities. The porous carbon-coated sulfur vacancy composite electrode material still has a sodium storage capacity of 125 mAh/g under the condition of a large current density of 10A/g, and when the current density is reduced to 0.1A/g from 10A/g again, the reversible capacity is recovered to 280mAh/g, which indicates that the porous carbon-coated sulfur vacancy composite electrode material has better rate performance.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. A porous carbon-coated sulfur vacancy composite electrode material is characterized in that: the composite electrode material is characterized in that sulfur vacancies exist in porous carbon-coated manganese sulfide particles, the particle size of the porous carbon-coated manganese sulfide particles is 10-50 nanometers, and the porous carbon-coated manganese sulfide composite material is prepared by heat treatment of a metal organic framework.
2. A preparation method of a porous carbon-coated sulfur vacancy composite electrode material is characterized by sequentially comprising the following steps of,
step 1: mixing inorganic manganese salt and terephthalic acid or 1, 3, 5-benzene tricarboxylic acid according to a molar ratio of 1: (0.8-5) respectively dissolving in a solvent to obtain an inorganic manganese salt solution and a terephthalic acid solution or a 1, 3, 5-benzene tricarboxylic acid solution, wherein the solvent is a mixture of deionized water and absolute ethyl alcohol;
step 2: uniformly mixing an inorganic manganese salt solution and a terephthalic acid solution or a 1, 3, 5-benzene trimethyl acid solution in a dropwise manner, and then standing and growing for 8-50 hours at 50-100 ℃ to obtain a primary product containing the manganese-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the manganese-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean manganese-based metal organic framework template;
and 4, step 4: and (3) mixing the clean manganese-based metal organic framework template obtained in the step (3) with a sulfur source in a mass ratio of 1: (1-5) after mixing, under the protection of high-purity argon, raising the temperature to 900 ℃ at the temperature-raising rate of 2-10 ℃/min, and keeping the temperature for 2-8 hours to carry out pyrolysis reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the porous carbon coated sulfur vacancy composite electrode material.
3. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: the inorganic manganese salt is manganese chloride, manganese acetate, manganese nitrate or manganese sulfate, and the sulfur source is thiourea or sublimed sulfur.
4. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: in the step 1, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid is 1: 0.8.
5. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: in the step 1, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid is 1: 3.
6. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: in the step 1, the molar ratio of the inorganic manganese salt to the terephthalic acid or the 1, 3, 5-benzene tricarboxylic acid is 1: 5.
7. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: the temperature in the step 2 is 100 ℃, and the standing growth time is 8 hours.
8. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: in the step 4, the manganese-based metal organic framework template and thiourea are subjected to pyrolysis reaction for 6 hours at the temperature of 600 ℃ at the heating rate of 2-10 ℃/min according to the mass ratio of 1: 4.
9. The preparation method of the porous carbon-coated sulfur vacancy composite electrode material according to claim 1, characterized in that: in the step 4, the manganese-based metal organic framework template and the sublimed sulfur are mixed according to the mass ratio of 1:5, the heating rate is 3 ℃/min, the temperature is increased to 900 ℃, and the pyrolysis reaction time is 2 hours.
10. A circular electrode is characterized in that the preparation method comprises the following steps: dispersing the porous carbon-coated sulfur vacancy composite electrode material prepared according to the claims 2 to 9, a binder sodium carboxymethyl cellulose and a conductive agent Super-P in deionized water to prepare slurry, wherein the mass ratio of the raw materials is as follows: binder sodium carboxymethylcellulose: conducting agent Super-P = 75: 15: 10, uniformly coating the slurry on a copper foil with the thickness of 9 μm, drying in vacuum for 12 hours, and cutting to obtain a circular electrode with the diameter of 14 mm.
CN202110134898.1A 2021-02-01 2021-02-01 Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material Pending CN112968173A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110134898.1A CN112968173A (en) 2021-02-01 2021-02-01 Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110134898.1A CN112968173A (en) 2021-02-01 2021-02-01 Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material

Publications (1)

Publication Number Publication Date
CN112968173A true CN112968173A (en) 2021-06-15

Family

ID=76272807

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110134898.1A Pending CN112968173A (en) 2021-02-01 2021-02-01 Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material

Country Status (1)

Country Link
CN (1) CN112968173A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114229902A (en) * 2021-12-20 2022-03-25 中原工学院 Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof
CN114700086A (en) * 2022-01-19 2022-07-05 华东理工大学 Preparation method of alpha-MnS catalyst, alpha-MnS catalyst obtained by preparation method and application of alpha-MnS catalyst
CN114824223A (en) * 2022-05-10 2022-07-29 扬州大学 MnS/carbon composite material with sulfur defect, and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106159234A (en) * 2016-08-25 2016-11-23 广东工业大学 Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell
CN106531999A (en) * 2016-11-25 2017-03-22 武汉理工大学 Embedded cobalt sulfide and porous carbon nanorod composite electrode material and preparation method and application thereof
WO2019173214A1 (en) * 2018-03-05 2019-09-12 Sabic Global Technologies B.V. Porous manganese dioxide-carbon hybrid hollow particles and uses thereof
CN110534739A (en) * 2019-08-19 2019-12-03 中南大学 Amorphous carbon-coated metal sulfide of one kind and preparation method thereof
CN110600707A (en) * 2019-09-25 2019-12-20 郑州大学 High-capacity electrode material for high-nitrogen-doped carbon-coated metal sodium sulfide secondary battery and application of high-capacity electrode material
CN111146424A (en) * 2019-12-30 2020-05-12 上海交通大学 Metal sulfide/carbon composite material and preparation method and application thereof
WO2020190560A2 (en) * 2019-03-07 2020-09-24 Cornell University Mof-sulfur materials and composite materials, methods of making same, and uses thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106159234A (en) * 2016-08-25 2016-11-23 广东工业大学 Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell
CN106531999A (en) * 2016-11-25 2017-03-22 武汉理工大学 Embedded cobalt sulfide and porous carbon nanorod composite electrode material and preparation method and application thereof
WO2019173214A1 (en) * 2018-03-05 2019-09-12 Sabic Global Technologies B.V. Porous manganese dioxide-carbon hybrid hollow particles and uses thereof
WO2020190560A2 (en) * 2019-03-07 2020-09-24 Cornell University Mof-sulfur materials and composite materials, methods of making same, and uses thereof
CN110534739A (en) * 2019-08-19 2019-12-03 中南大学 Amorphous carbon-coated metal sulfide of one kind and preparation method thereof
CN110600707A (en) * 2019-09-25 2019-12-20 郑州大学 High-capacity electrode material for high-nitrogen-doped carbon-coated metal sodium sulfide secondary battery and application of high-capacity electrode material
CN111146424A (en) * 2019-12-30 2020-05-12 上海交通大学 Metal sulfide/carbon composite material and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114229902A (en) * 2021-12-20 2022-03-25 中原工学院 Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof
CN114229902B (en) * 2021-12-20 2023-09-15 中原工学院 Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof
CN114700086A (en) * 2022-01-19 2022-07-05 华东理工大学 Preparation method of alpha-MnS catalyst, alpha-MnS catalyst obtained by preparation method and application of alpha-MnS catalyst
CN114700086B (en) * 2022-01-19 2023-08-18 华东理工大学 Preparation method of alpha-MnS catalyst, alpha-MnS catalyst obtained by preparation method and application of alpha-MnS catalyst
CN114824223A (en) * 2022-05-10 2022-07-29 扬州大学 MnS/carbon composite material with sulfur defect, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107331867B (en) Preparation method of nitrogen-doped porous carbon material used as negative electrode of sodium-ion battery
CN105720251B (en) A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof
Chu et al. NiO nanocrystals encapsulated into a nitrogen-doped porous carbon matrix as highly stable Li-ion battery anodes
CN110571432A (en) element-doped biomass hard carbon negative electrode material for sodium ion battery, preparation method and sodium ion battery
CN112968173A (en) Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material
CN108269982B (en) Composite material, preparation method thereof and application thereof in lithium ion battery
CN108232142B (en) Zinc sulfide/graphene composite material, and preparation method and application thereof
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN108172770B (en) Carbon-coated NiP with monodisperse structural featuresxNano composite electrode material and preparation method thereof
Jiang et al. A novel CoO hierarchical morphologies on carbon nanofiber for improved reversibility as binder-free anodes in lithium/sodium ion batteries
CN108767203B (en) Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof
CN112117444A (en) Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery
CN108899499B (en) Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery
CN108400296B (en) Heterogeneous element doped ferroferric oxide/graphene negative electrode material
CN109950503B (en) CoMoOxPreparation method of/carbon/sulfur composite nano material, lithium ion battery cathode and lithium ion half battery
Lan et al. Nano-MnS@ N doped lignite derived carbon composites as superior anode material for sodium-ion batteries
CN113036097B (en) Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof
CN108110231B (en) Carbon-coated Fe4N nano composite material, preparation method and application thereof
CN115084465B (en) Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof
CN109841812B (en) Ternary nickel cobaltate lithium ion battery cathode material with sandwich structure and preparation method thereof
CN108110235B (en) Hollow nickel-nickel oxide nanoparticle/porous carbon nanosheet layer composite material and preparation method and application thereof
Zeng et al. Microwave-assisted synthesis of Cr 3 C 2@ C core shell structure anchored on hierarchical porous carbon foam for enhanced polysulfide adsorption in Li-S batteries
CN114944476B (en) MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof
Zou et al. CNT network crosslinked by metal Co2+ for stabilizing SnO2 anodes
CN115425209A (en) Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20210615

RJ01 Rejection of invention patent application after publication