CN107739031B - Method for preparing lithium ion carbon negative electrode material from mushroom residue waste - Google Patents

Method for preparing lithium ion carbon negative electrode material from mushroom residue waste Download PDF

Info

Publication number
CN107739031B
CN107739031B CN201710971891.9A CN201710971891A CN107739031B CN 107739031 B CN107739031 B CN 107739031B CN 201710971891 A CN201710971891 A CN 201710971891A CN 107739031 B CN107739031 B CN 107739031B
Authority
CN
China
Prior art keywords
nickel
dregs
mushroom
porous carbon
hierarchical porous
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.)
Active
Application number
CN201710971891.9A
Other languages
Chinese (zh)
Other versions
CN107739031A (en
Inventor
唐晶晶
周向阳
廖群超
杨娟
李晨
蒋敏
王倩
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.)
Dali Chenyu Energy Storage New Material Co ltd
Original Assignee
Central South 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 Central South University filed Critical Central South University
Priority to CN201710971891.9A priority Critical patent/CN107739031B/en
Publication of CN107739031A publication Critical patent/CN107739031A/en
Application granted granted Critical
Publication of CN107739031B publication Critical patent/CN107739031B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a method for preparing multi-element doped hierarchical porous carbon by taking mushroom residue waste as a raw material, and the method is applied to a lithium battery cathode material. The method comprises the following steps: drying and ball-milling single mushroom residue waste, mixing the mushroom residue waste with metal salt and inorganic base, calcining the mixture at a high temperature, and removing metal impurities by using inorganic acid to obtain multi-element doped hierarchical porous carbon. The hierarchical porous carbon prepared by the method has multi-element doping, and simultaneously has rich micropores, mesopores and macropores, and is particularly suitable for being applied to lithium ion cathode materials. The method has the advantages of wide raw material source, simple process, convenient operation, low cost, excellent performance of the obtained product and easy expanded production.

Description

Method for preparing lithium ion carbon negative electrode material from mushroom residue waste
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for preparing a carbon negative electrode material for a lithium ion battery by taking mushroom dreg waste as a raw material.
Background
As a green energy storage device, the lithium ion battery has a series of advantages of high energy density, high open circuit voltage, green environmental protection, and the like, and has been widely applied to portable electronic devices, such as mobile phones, notebooks, portable cameras, and the like. The graphite carbon material is the main commercial negative electrode material of the current lithium ion battery, but the theoretical specific capacity of the graphite is only 372mAh g-1It is difficult to meet the demand for high energy density in the future. Research shows that the porous carbon material and element doping can provide more active sites for lithium ions, so that the reversible specific capacity of the carbon material is effectively improved. Chinese patent CN 104332596 reports that melamine, benzene dicarboxaldehyde, carbon nano tube and dimethyl sulfoxide are adopted as raw materials to prepare the nano-composite material by adopting a vacuum heat treatment methodA nitrogen-doped porous carbon/carbon nanotube composite. Huawei Song et al uses organic matter as precursor, and prepares nitrogen-doped porous carbon (Acs Applied Materials) by template method&Interfaces,2014,6(23): 21661-8). When the materials are used as the lithium ion battery cathode materials, the materials have higher specific capacity. However, in the prior art, the preparation of the element-doped porous carbon material usually requires a special carbon source and a doping element precursor as raw materials, so that the cost is high, the operation is complex, and the use of the element-doped porous carbon material in large-scale production is limited.
The antibiotic dregs are waste material produced in the production of antibiotic, including terramycin dregs, penicillin dregs, cephalosporin dregs, etc. and their main components are crude protein, crude fat, crude fiber, amino acid, etc. and contain great amount of C, N, O and metal elements, such as Ca, Fe, Zn, Mg, etc. China is a big antibiotic country and generates a large amount of fungus dreg waste every year. In order to prevent a large amount of the smoke from accumulating, incineration and burial measures are mainly taken for treatment, however, smoke generated by incineration pollutes air, and burial makes the smoke dissolved in underground water, so that water pollution is caused. Meanwhile, the two processing methods are also waste of resources. How to effectively and reasonably treat the mushroom dreg waste materials becomes a problem to be treated urgently at present. In fact, the mushroom dregs contain more than 40% of carbon components, so that carbon materials with certain functions can be obtained through calcination, and elements such as nitrogen, phosphorus and the like in certain proportion contained in the mushroom dregs can be directly used as sources of beneficial doping elements. So far, the related technology for preparing the lithium ion carbon negative electrode material by taking the mushroom dreg waste as the raw material is rarely reported.
Disclosure of Invention
The invention mainly aims to solve the technical problems at present and provides a simple method for preparing multi-element doped hierarchical porous carbon serving as a lithium ion battery cathode material by taking mushroom residue waste as a raw material.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste, which comprises the following steps of;
step one
Uniformly mixing the dried mushroom residue powder with metal salt and inorganic base to obtain a mixture; in the mixture, the mass ratio of the dried mushroom residue powder to the metal salt to the inorganic base is 15-2: 1: 1-8; the mushroom dreg powder is selected from one of terramycin mushroom dreg powder, cephalosporin mushroom dreg powder and penicillin mushroom dreg powder;
step two
Calcining the mixture obtained in the step one at a high temperature under a protective atmosphere; obtaining a carbonized mixture; the high-temperature calcination temperature is 700-1100 ℃;
step three
Placing the carbonized mixture obtained in the step two in a solution containing inorganic acid, soaking for at least 6h, filtering to obtain filter residue, and cleaning the filter residue until the pH value of the washing liquid is 6-8; obtaining a semi-finished product; and drying the obtained semi-finished product to obtain the multi-element doped hierarchical porous carbon cathode material, namely the lithium ion carbon cathode material.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, wherein in dried mushroom residue powder, the carbon content is 20-50 wt%, the nitrogen content is 5-15 wt%, the oxygen content is 10-30 wt%, the phosphorus content is 0.1-15 wt%, and the sulfur content is 0.1-15 wt%;
the invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste, wherein the dried mushroom dreg powder is prepared by the following scheme:
baking the mushroom residue waste in a vacuum drying oven at 80-120 ℃ for 12-36 h, removing water in the mushroom residue waste, and then ball-milling the dried mushroom residue waste for 6-12 h to obtain dried mushroom residue powder; the particle size of the dried mushroom dreg powder is 5-50 mu m.
The invention relates to a method for preparing a lithium ion carbon negative electrode material from mushroom residue waste, wherein the mass ratio of dried mushroom residue powder, metal salt and inorganic base in a mixture is 10-3: 1: 1-8.
The invention relates to a method for preparing a lithium ion carbon negative electrode material from mushroom residue waste, wherein when mushroom residue powder is terramycin mushroom residue powder, the mass ratio of dried mushroom residue powder, metal salt and inorganic base in the mixture is 10-3: 1: 1-5. In a further preferable mode, the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base in the mixture is 7-5: 1: 2-4. Most preferably, the mass ratio of the dried mushroom dreg powder to the metal salt to the inorganic base in the mixture is 6:1: 3.
According to the method for preparing the lithium ion carbon negative electrode material by using the mushroom residue waste, when the mushroom residue powder is penicillin mushroom residue powder, the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base in the mixture is 15-7: 2: 2-11. In a further preferable mode, the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base in the mixture is 13-5: 2-1: 4-6. Most preferably, the mass ratio of the dried mushroom dreg powder to the metal salt to the inorganic base in the mixture is 11:2: 6.
According to the method for preparing the lithium ion carbon negative electrode material by using the mushroom residue waste, when the mushroom residue powder is cephalosporin mushroom residue powder, the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base in the mixture is 20-6: 2: 3-15. In a further preferable mode, the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base in the mixture is 15-9: 2: 5-10. Most preferably, the mass ratio of the dried mushroom dreg powder to the metal salt to the inorganic base in the mixture is 12:2: 7.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, which comprises the following steps of firstly, preparing dry mushroom residue powder, metal salt and inorganic base according to set components, then placing the prepared dry mushroom residue powder, metal salt and inorganic base into water, uniformly stirring, heating to 80-100 ℃, and continuously stirring until the water is evaporated to dryness; obtaining the mixture; the stirring is magnetic stirring, and the rotating speed of the magnetic stirring is 300-1000 rmin-1。
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, wherein the metal salt is water-soluble metal salt, and the cation is selected from at least one of iron, copper, zinc, nickel, cobalt and manganese; the inorganic alkali is one or two of sodium hydroxide and potassium hydroxide. Preferably, the metal salt is selected from chloride and/or nitrate of at least one of iron, copper, zinc, nickel, cobalt, manganese.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, which comprises the following steps of in a second step, calcining a mixture obtained in the first step at a high temperature for 1-5 hours in a protective atmosphere; obtaining a carbonized mixture; the high-temperature calcination temperature is 700-1100 ℃.
According to the method for preparing the lithium ion carbon negative electrode material by using the mushroom dreg waste, in the second step, the mixture obtained in the first step is calcined at high temperature for 1-5 hours in a protective atmosphere; obtaining a carbonized mixture; the high-temperature calcination temperature is 700-1100 ℃; the protective atmosphere is at least one selected from nitrogen atmosphere, argon atmosphere and hydrogen-argon mixed atmosphere, and the flow speed of the protective gas is 0.2-2L/min during high-temperature calcination. In the industrial application, the temperature is raised from room temperature to 700-1100 ℃, preferably 980-1050 ℃, and more preferably 1000 ℃ at a temperature raising rate of 1-10 ℃/min.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, which comprises the step two, wherein the protective atmosphere is at least one selected from nitrogen atmosphere, argon atmosphere and hydrogen-argon mixed atmosphere, and the flow rate of the protective gas is 0.2-2L/min during high-temperature calcination.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste, which comprises the following steps of, in the third step, using inorganic acid as hydrochloric acid and/or sulfuric acid; in the solution containing the inorganic acid; the concentration of the inorganic acid is 0.1-3 mol/L.
In the third step, the inorganic acid is hydrochloric acid and/or sulfuric acid; in the solution containing the inorganic acid, the concentration of the inorganic acid is 0.1-3 mol/L.
The invention relates to a method for preparing a lithium ion carbon negative electrode material by using mushroom residue waste, which comprises the following steps of putting a carbonized mixture obtained in the step two into a solution containing inorganic acid, stirring and soaking for 6-12 hours, filtering to obtain filter residues, and cleaning the filter residues until the pH value of a washing solution is 6-8; obtaining a semi-finished product; and drying the obtained semi-finished product at 60-100 ℃ to obtain the multi-element doped hierarchical porous carbon cathode material, namely the lithium ion carbon cathode material.
In the third step, the doping elements in the multi-element doped hierarchical porous carbon negative electrode material comprise one or more of nitrogen, oxygen, phosphorus and sulfur. In a further preferable scheme, the content of nitrogen, oxygen, phosphorus and sulfur in the multi-element doped hierarchical porous carbon negative electrode material is 0.1-10 wt%, and 0.1-10 wt%.
The invention relates to a method for preparing a lithium ion carbon negative electrode material from mushroom residue waste, wherein the lithium ion carbon negative electrode material has a first discharge specific capacity of 812-1194 mAh/g when the current density is 0.1A/g, and the reversible capacity of 682-982 mAh/g is still maintained after 100 times of circulation. After optimization, the first discharge specific capacity is 900-1194 mAh/g, and after 100 cycles, the reversible capacity still keeps 730-982 mAh/g.
The principle of the invention is as follows: the mushroom dreg waste contains a large amount of carbon, nitrogen, oxygen, phosphorus, sulfur and other elements, the carbon element is carbonized through calcination at 700-1100 ℃ in a protective atmosphere, and the nitrogen, the oxygen, the phosphorus and the sulfur can be partially remained in a doped form, so that the multi-element doped carbon material is obtained. In addition, a suitable amount of inorganic base reacts with the carbon material during the high temperature calcination process, causing the carbon material to produce a large number of pores, including macropores, mesopores and micropores. Meanwhile, a proper amount of metal salt can also react with carbon in the high-temperature calcination process to generate a metal simple substance and carbon dioxide, so that a large amount of micropores and mesopores are further formed in the carbon material, and the generated metal simple substance has the function of catalyzing graphitization, so that the ordered degree of atomic arrangement of the mushroom residue carbon can be obviously improved, and the conductivity is improved. According to the invention, by controlling the mass ratio of the dried mushroom residue powder, the metal salt and the inorganic base, under the synergistic effect of other condition parameters, the multi-element doped hierarchical porous carbon with reasonable pore size distribution and excellent conductivity is obtained, and when the multi-element doped hierarchical porous carbon is applied to the lithium ion battery cathode material, excellent electrical properties are shown. The invention has the beneficial effects that:
(1) the mushroom dreg waste material used as the raw material for preparing the multi-element doped hierarchical porous carbon has wide sources, belongs to solid waste in the pharmaceutical industry, is harmful substances which are urgently needed to be treated and are difficult to treat, and is prepared into a new energy material with high added value by a simple and effective technical scheme, so that the invention has high economic benefit and social benefit.
(2) The mushroom dreg waste material used for preparing the multi-element doped hierarchical porous carbon contains a certain amount of elements such as nitrogen, oxygen, sulfur, phosphorus and the like, so that doping by adding a doping agent is not needed. The element doping can not only improve the lithium storage capacity of the carbon material, but also be used as an active site for lithium storage, thereby greatly improving the reversible specific capacity of the carbon material.
(3) In the process of preparing the multi-element doped hierarchical porous carbon, a proper amount of inorganic alkali and metal salt are used for pore forming on the carbon material, so that the obtained carbon material has abundant and reasonable micropores, mesopores and macropores, wherein the micropores can provide more active sites of lithium ions, the mesopores are beneficial to shortening the transmission distance of the lithium ions, and the macropores can accommodate a large amount of electrolyte. In addition, a metal simple substance obtained by the reaction of a proper amount of metal salt and the carbon material can play a role in catalyzing the graphitization of the carbon material at high temperature, and the atomic arrangement order degree of the carbon material is improved, so that the electric conductivity of the carbon material is improved, and the comprehensive electrochemical performance of the cathode material is improved from multiple aspects.
(4) The method has the advantages of simple process, convenient operation, environmental protection, low cost, high yield and easy realization of large-scale production.
Description of the drawings:
fig. 1 is a scanning electron microscope image of the multi-doped hierarchical porous carbon prepared in example 1 of the present invention.
Fig. 2 is a nitrogen isothermal adsorption and desorption curve of the multi-doped hierarchical porous carbon prepared in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of the multi-doped hierarchical porous carbon prepared in example 1 of the present invention.
Fig. 4 is a graph of the cycling profile of a cell assembled from a multi-doped hierarchical pore carbon material prepared in example 1 of the present invention.
As can be seen from fig. 1, the prepared material has a distinct porous sheet-like structure.
As can be seen from FIG. 2, the prepared material has hierarchical pore characteristics of micropores, mesopores and macropores.
As can be seen from fig. 3, the prepared material was mainly composed of C, N, O three elements.
As can be seen from FIG. 4, the material prepared by the invention has high reversible specific capacity and excellent cycle performance when being used as a lithium ion battery cathode.
Detailed Description
The present invention will be further described with reference to examples, but the embodiments of the present invention are not limited thereto.
In the examples of the present invention and the comparative examples, the dried oxytetracycline used had a carbon content of 40 wt%, a nitrogen content of 9 wt%, an oxygen content of 32 wt%, a phosphorus content of 1.2 wt%, and a sulfur content of 0.8 wt%.
The dry penicillin fungi residue contains 43 wt% of carbon, 9 wt% of nitrogen, 35 wt% of oxygen, 1.1 wt% of phosphorus and 1.5 wt% of sulfur.
The cephalosporin dregs contain carbon 44 wt%, nitrogen 11 wt%, oxygen 37 wt%, phosphorus 0.7 wt% and sulfur 1.1 wt%.
Example 1
(1) Placing terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, then carrying out ball milling on the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 micrometers (2) mixing a certain amount of terramycin mushroom dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to the mass ratio of 10:1:1, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at the air flow speed of 1L/min and the heating rate of 5 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon; (4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 909mAh/g, the first coulombic efficiency is 74.3%, and after 100 cycles, the reversible capacity is still maintained at 712 mAh/g.
Example 2
(1) Placing terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, then carrying out ball milling on the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 micrometers (2) mixing a certain amount of terramycin mushroom dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to the mass ratio of 6:1:3, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at the air flow speed of 1L/min and the heating rate of 5 ℃/min under the nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon; (4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
The multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method has high specific capacity and high rate performance, when the current density is 0.1A/g, the first discharge specific capacity is 1169mAh/g, the first coulombic efficiency is 79.3%, and after 100 cycles, the reversible capacity is still 960 mAh/g.
Example 3
(1) Placing terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, then carrying out ball milling on the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 micrometers (2) mixing a certain amount of terramycin mushroom dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to the mass ratio of 3:1:5, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion cathode material obtained by the method is 0.1A/g, the first discharge specific capacity is 944mAh/g, the first coulombic efficiency is 68.3%, and after 100 cycles, the reversible capacity is still maintained at 782 mAh/g.
It can be seen from examples 1, 2, and 3 that the product performance obtained by the preferred embodiment of the present invention is significantly improved.
Comparative example 1
(1) Placing the terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, then carrying out ball milling on the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 microns, (2) mixing a certain amount of terramycin mushroom dregs obtained in the step (1) and nickel chloride in an aqueous solution according to the mass ratio of 6:1, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride and the mushroom dreg;
(3) heating the uniform mixture of the nickel chloride and the mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing metallic nickel and hierarchical porous carbon;
(4) soaking the mixture containing the metallic nickel and the hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 529mAh/g, the first coulombic efficiency is 65.6%, and after 100 cycles, the reversible capacity is only 422 mAh/g.
It can be seen from examples 1, 2, 3 and comparative example 1 that the performance of the product obtained by activating the pore-forming agent without adding alkali is far inferior to the scheme designed by the present invention.
Comparative example 2
(1) Placing terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours to remove water, then carrying out ball milling on the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 micrometers (2), mixing a certain amount of terramycin mushroom dregs obtained in the step (1) and sodium hydroxide in an aqueous solution according to the mass ratio of 2:1, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the sodium hydroxide and the mushroom dregs;
(3) heating the uniform mixture of the sodium hydroxide and the bacterial residues obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing sodium carbonate and hierarchical porous carbon;
(4) soaking the mixture containing the sodium carbonate and the hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water to be neutral;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
The multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method has high specific capacity and high rate performance, when the current density is 0.1A/g, the first discharge specific capacity is 721mAh/g, the first coulombic efficiency is 63.3%, and after 100 cycles, the reversible capacity is kept at 582 mAh/g.
It can be seen from examples 1, 2, 3 and comparative example 2 that the performance of the product obtained by activating the pore-forming agent without adding nickel chloride (i.e., metal salt) is far inferior to the scheme designed by the present invention.
Comparative example 3
Other conditions were consistent with example 3, except that: the mass ratio of the terramycin bacterial residues to the nickel chloride to the sodium hydroxide is 20:1: 1; when the current density of the obtained product is 0.1A/g, the first discharge specific capacity of the product is only 432mAh/g, the first coulombic efficiency is 55.9%, and the reversible capacity of the product is only 209mAh/g after 100 cycles.
Comparative example 4
Other conditions were consistent with example 3, except that: the mass ratio of the terramycin bacterial residues to the nickel chloride to the sodium hydroxide is 2:1: 5; when the current density of the obtained product is 0.1A/g, the first discharge specific capacity of the product is only 478mAh/g, the first coulombic efficiency is 42.8%, and the reversible capacity of the product is only 187mAh/g after 100 cycles.
It can be seen from examples 1, 2 and 3 and comparative examples 4 and 5 that without the design according to the invention, the resulting product properties are markedly reduced.
Example 4
1) Baking penicillin fungi residues in a vacuum drying oven at 100 ℃ for 24 hours to remove water, and then ball-milling the obtained dried fungi residue waste for 6 hours to obtain fungi residue powder with the average particle size of about 25 mu m;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 15:2:2, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
The multi-element doped hierarchical porous carbon lithium ion negative electrode material obtained by the method has high specific capacity and high rate performance, when the current density is 0.1A/g, the first discharge specific capacity is 954mAh/g, the first coulombic efficiency is 68.3%, and after 100 cycles, the reversible capacity is still 732 mAh/g.
Example 5
1) Baking penicillin fungi residues in a vacuum drying oven at 100 ℃ for 24 hours to remove water, and then ball-milling the obtained dried fungi residue waste for 6 hours to obtain fungi residue powder with the average particle size of about 25 mu m;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 7:2:11, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon; (ii) a
(4) Soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
The multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method has high specific capacity and high rate performance, when the current density is 0.1A/g, the first discharge specific capacity is 912mAh/g, the first coulombic efficiency is 70.3%, and after 100 cycles, the reversible capacity is still maintained at 782 mAh/g.
Example 6
(1) Putting the penicillin fungi residues into a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, and then ball-milling the obtained dried fungi residue waste for 6 hours to obtain fungi residue powder with the average particle size of about 25 microns;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 11:2:6, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 1194mAh/g, the first coulombic efficiency is 78.3%, and after 100 cycles, the reversible capacity is kept at 982 mAh/g.
By comparing the examples 4, 5 and 6, it can be seen that the product performance is significantly improved by adopting the preferred scheme of the invention.
Example 7
(1) Placing the cephalosporin dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours to remove water, and then ball-milling the obtained dried dregs waste for 6 hours to obtain dregs powder with the average particle size of about 30 mu m;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 20:2:3, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 864mAh/g, the first coulombic efficiency is 68.3%, and after 100 cycles, the reversible capacity is kept at 732 mAh/g.
Example 8
(1) Placing the cephalosporin dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours to remove water, and then ball-milling the obtained dried dregs waste for 6 hours to obtain dregs powder with the average particle size of about 30 mu m;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 6:2:15, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 812mAh/g, the first coulombic efficiency is 62.5%, and after 100 cycles, the reversible capacity is kept at 682 mAh/g.
Example 9
(1) Baking the cephalosporin dregs in a vacuum drying oven at 100 ℃ for 24 hours to remove water, and then ball-milling the obtained dried dregs waste for 6 hours to obtain dregs powder with the average particle size of about 25 mu m;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 12:2:7, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, carrying out vacuum filtration, and washing with deionized water until the pH is 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
When the current density of the multi-element doped hierarchical pore carbon lithium ion negative electrode material obtained by the method is 0.1A/g, the first discharge specific capacity is 1109mAh/g, the first coulombic efficiency is 76.2%, and the reversible capacity is maintained at 962mAh/g after 100 cycles.
By comparing the examples 7, 8 and 9, it can be seen that the product performance is significantly improved by adopting the preferred scheme of the invention.

Claims (3)

1. A method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste is characterized by comprising the following steps: comprises the following steps;
(1) placing the terramycin mushroom dregs in a vacuum drying oven at 100 ℃ for baking for 24 hours to remove moisture, and then ball-milling the obtained dried mushroom dreg waste for 6 hours to obtain mushroom dreg powder with the average particle size of about 20 mu m, wherein the carbon content in the dried terramycin mushroom dregs is 40 wt%, the nitrogen content is 9 wt%, the oxygen content is 32 wt%, the phosphorus content is 1.2 wt%, and the sulfur content is 0.8 wt%;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 6:1:3, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is = 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
2. A method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste is characterized by comprising the following steps: comprises the following steps;
(1) putting the penicillin fungi residues into a vacuum drying oven at 100 ℃ for baking for 24 hours, removing water, and then ball-milling the obtained dried fungi residue waste for 6 hours to obtain fungi residue powder with the average particle size of about 25 microns; the carbon content of the used dry penicillin fungi residue is 43 wt%, the nitrogen content is 9 wt%, the oxygen content is 35 wt%, the phosphorus content is 1.1 wt%, and the sulfur content is 1.5 wt%;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 11:2:6, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is = 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
3. A method for preparing a lithium ion carbon negative electrode material by using mushroom dreg waste is characterized by comprising the following steps: comprises the following steps;
(1) baking the cephalosporin dregs in a vacuum drying oven at 100 ℃ for 24 hours to remove water, and then ball-milling the obtained dried dregs waste for 6 hours to obtain dregs powder with the average particle size of about 25 mu m; the cephalosporin dregs contain 44 wt% of carbon, 11 wt% of nitrogen, 37 wt% of oxygen, 0.7 wt% of phosphorus and 1.1 wt% of sulfur;
(2) mixing a certain amount of the oxytetracycline bacterial dregs obtained in the step (1) with nickel chloride and sodium hydroxide in an aqueous solution according to a mass ratio of 12:2:7, and continuously stirring at 80 ℃ until the water is evaporated to dryness to obtain a uniform mixture of the nickel chloride, the nickel hydroxide, the sodium hydroxide and the bacterial dregs;
(3) heating the uniform mixture of nickel chloride, nickel hydroxide, sodium hydroxide and mushroom dregs obtained in the step (2) to 1000 ℃ at an air flow rate of 1L/min and a heating rate of 5 ℃/min under a nitrogen atmosphere, and preserving heat for 2h to obtain a mixture containing nickel, sodium chloride and hierarchical porous carbon;
(4) soaking the mixture containing nickel, sodium chloride and hierarchical porous carbon obtained in the step (3) in a hydrochloric acid solution with the molar concentration of 1mol/L, stirring for 6 hours, performing vacuum filtration, and washing with deionized water until the pH is = 7;
(5) and (4) drying the filter cake obtained in the step (4) at 80 ℃ to finally obtain the multi-doped hierarchical porous carbon cathode material.
CN201710971891.9A 2017-10-18 2017-10-18 Method for preparing lithium ion carbon negative electrode material from mushroom residue waste Active CN107739031B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710971891.9A CN107739031B (en) 2017-10-18 2017-10-18 Method for preparing lithium ion carbon negative electrode material from mushroom residue waste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710971891.9A CN107739031B (en) 2017-10-18 2017-10-18 Method for preparing lithium ion carbon negative electrode material from mushroom residue waste

Publications (2)

Publication Number Publication Date
CN107739031A CN107739031A (en) 2018-02-27
CN107739031B true CN107739031B (en) 2021-07-16

Family

ID=61237681

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710971891.9A Active CN107739031B (en) 2017-10-18 2017-10-18 Method for preparing lithium ion carbon negative electrode material from mushroom residue waste

Country Status (1)

Country Link
CN (1) CN107739031B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993382B (en) * 2018-06-25 2021-09-07 湖南烯富环保科技有限公司 Defluorination material based on mushroom dregs and regeneration method thereof
CN109626370A (en) * 2019-01-21 2019-04-16 青岛科技大学 The preparation and its application of biomass-based porous carbon materials based on sycamore seed
CN109879266B (en) * 2019-03-05 2020-12-22 中南大学 Preparation method of porous carbon-based composite material
CN111003710A (en) * 2020-01-17 2020-04-14 宿州学院 Method for preparing nitrogen-doped graded porous carbon by using waste medicine residues and application of method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502630A (en) * 2011-11-30 2012-06-20 河北科技大学 Method for preparing activated carbon from penicillin or terramycin strain residues
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material
CN105316069A (en) * 2015-11-06 2016-02-10 江西康丰生物科技有限公司 Technology for refining biochar through waste fungus residue recovery
WO2016143439A1 (en) * 2015-03-06 2016-09-15 国立大学法人大阪大学 Porous body including bacterial cellulose and polymer, and method of manufacturing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502630A (en) * 2011-11-30 2012-06-20 河北科技大学 Method for preparing activated carbon from penicillin or terramycin strain residues
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material
WO2016143439A1 (en) * 2015-03-06 2016-09-15 国立大学法人大阪大学 Porous body including bacterial cellulose and polymer, and method of manufacturing same
CN105316069A (en) * 2015-11-06 2016-02-10 江西康丰生物科技有限公司 Technology for refining biochar through waste fungus residue recovery

Also Published As

Publication number Publication date
CN107739031A (en) 2018-02-27

Similar Documents

Publication Publication Date Title
CN107739031B (en) Method for preparing lithium ion carbon negative electrode material from mushroom residue waste
CN109037625B (en) Composite material of hierarchical porous carbon and cobalt sulfide, and preparation method and application thereof
CN109243853B (en) Method for preparing high-specific-capacity nano composite material by adopting double templates
CN104409733B (en) Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof
CN110518245B (en) Carbon material prepared from water-absorbing resin and application of carbon material in positive electrode of lithium-sulfur battery
CN110648854B (en) Boron-nitrogen co-doped carbon/manganese oxide composite nanosheet material, and preparation method and application thereof
CN104495788A (en) Preparation method of porous carbon
CN112794324B (en) High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof
CN107732209B (en) Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste
CN110767901A (en) Preserved plum-shaped iron diselenide electrode material and preparation method and application thereof
CN103832997A (en) Graphene/carbon black composite material, preparation method and application thereof
CN114956037A (en) Carbon material for sodium ion battery negative electrode, preparation method of carbon material, sodium ion battery negative electrode piece and sodium ion battery
CN110668438A (en) Novel porous carbon electrode material for capacitive deionization technology and application thereof
CN110734097B (en) ZIF 67-containing derived composite carbon material lithium-sulfur battery positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and lithium-sulfur battery
CN113201759B (en) Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof
CN115036516A (en) Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof
CN109626444B (en) Porous channel submicron spherical FeS2Preparation method of (1)
CN109301246B (en) Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode
CN114944480B (en) Preparation method of honeycomb porous tin-carbon composite material
CN111302326A (en) Nitrogen-doped hierarchical porous carbon material for lead-carbon battery and preparation method thereof
CN114695861B (en) Preparation method of sulfur and nitrogen co-doped porous carbon material, prepared carbon material and application thereof
CN104269223A (en) Method for preparing electrode materials by using electroplating sludge and eggshell membranes
CN114530598A (en) Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof
CN112480422A (en) Preparation method and electrical property test method of Mofs composite material
CN112265977A (en) Method for preparing porous hollow carbon material by etching

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
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230714

Address after: 672100 East of Industrial Avenue, Yanpo Area, Fortune Industrial Park, Xiangcheng Town, Xiangyun County, Dali Bai Autonomous Prefecture, Yunnan Province

Patentee after: Dali Chenyu energy storage new material Co.,Ltd.

Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932

Patentee before: CENTRAL SOUTH University

TR01 Transfer of patent right