CN111697228B - Preparation method of fluorine intercalation graphitized carbon material - Google Patents
Preparation method of fluorine intercalation graphitized carbon material Download PDFInfo
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- CN111697228B CN111697228B CN202010376817.4A CN202010376817A CN111697228B CN 111697228 B CN111697228 B CN 111697228B CN 202010376817 A CN202010376817 A CN 202010376817A CN 111697228 B CN111697228 B CN 111697228B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of a fluorine intercalation graphitized carbon material, which is implemented according to the following steps: (1) Uniformly mixing an amino compound and a layered compound, heating to 250-400 ℃ by a program, keeping for several hours, and rapidly cooling to room temperature to obtain a thermal intercalation precursor compound: (2) Stirring the precursor compound and a mixed solution of formaldehyde, acetaldehyde and phosphoric acid under a heating condition for reaction, performing suction filtration, washing and other steps on the reacted solution, and performing vacuum drying; heating the obtained solid material to 500-650 ℃ in air, and slowly cooling to room temperature; (3) And (4) carrying out centrifugal separation on the obtained product for multiple times, washing the product for multiple times by using a washing solution, and drying the product in vacuum. To obtain the fluorine intercalation graphitized carbon composite material. The preparation method is simple in preparation process, low in cost and easy for large-scale production, and the synthesized material has good lithium ion battery performance.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of a high-efficiency fluorine intercalation graphitized carbon material.
Background
Nowadays, the energy problem has become a serious worldwide problem, and has also become a big problem that hinders the continuous development of the science and technology in the world. Therefore, in order to further promote sustainable development, various advanced energy sources with high efficiency, low pollution and low cost are vigorously developed, and the development is urgent. Among them, the lithium ion battery has received much attention from people due to its advantages such as high energy storage density and long service life. However, with the mass production of various portable electronic devices and the rapid development of electric vehicles, the requirements for the capacity and the cycle performance of lithium ion batteries become more and more strict, and the conventional lithium ion batteries cannot meet the social requirements, which requires that the next generation of lithium ion batteries must have lower cost and high safety performance, especially have the characteristics of high capacity, high power and high energy density.
In the fields of fuel cell catalysts, electrodes of supercapacitors, cathodes of lithium ion batteries and the like, nitrogen and fluorine co-doped carbon materials are widely concerned as high-performance active material materials. Various morphologies including nanotubes (CNTs), carbon Nanofibers (NFs), nanospheres (NPs), and various structures including two-dimensional (2D) graphite materials and three-dimensional (3D) microporous carbon hybrids have also been widely developed. Among the various carbon anode materials described above, two-dimensional nanostructures are increasingly being used in energy storage devices. For example, two-dimensional graphitized carbon materials exhibit superior performance to pure graphite in terms of extended lithium storage capacity and extended cycle stability. The excellent electrochemical performance is attributed to the advantages of a larger specific surface area brought by the 2D nano structure, better contact with an electrolyte solution, a shorter lithium ion diffusion path, more effective electron transmission along a plane surface in the long-term charge and discharge process and the like.
Numerous research results indicate that many different functions may be exhibited in different types of nitrogen atom-doped carbon materials. The nitrogen atom has the atom size similar to that of the carbon atom, five valence electrons of the nitrogen atom can be firmly bonded with the carbon atom, when the nitrogen atom is doped in the carbon material, the band gap structure of the material can be adjusted, the conductivity of the material is enhanced, a plurality of defects and active sites are introduced at the same time, so that the nitrogen atom can be effectively combined with lithium ions, the wettability of the electrode material in an electrolyte solution can be improved, and a new structure with unique physical and chemical properties is often introduced.
In recent years, fluorine-doped carbon materials have attracted much attention because of their excellent properties exhibited in lithium ion batteries. At present, the introduction of F element is mainly realized by adopting a hydrothermal reaction with a fluorine-containing substance under high temperature and high pressure. However, such a method is not only high in energy consumption, but also has a very limited amount of passing doping, resulting in difficulty in mass production. Therefore, the method has important practical significance for introducing F and N doping through a simple and efficient mode,
as an emerging new method for obtaining functional materials, the method of confined space synthesis can construct materials with more novel structures by utilizing organic assembly of a guest and a host on the premise of keeping basic structural characteristics and performances of a host compound. In addition, the host material can be chemically modified and grafted with the guest material, so that more excellent material performance is realized, and a new idea is provided for developing an electrochemical energy storage material with high capacity, high multiplying power and long service life. The research content of the invention aims to synthesize a graphitized carbon lithium ion battery material beneficial to fluorine intercalation by the assistance of a limited space system.
Disclosure of Invention
The invention aims to solve the problems of high energy consumption, low fluorine intercalation amount, poor lithium battery performance and the like in the preparation of the conventional fluorine intercalation graphitized carbon material used in a lithium battery cathode material, and provides a preparation method of a fluorine intercalation porous nitrogen-doped carbon material with the characteristics of high intercalation amount, high activity, large specific surface area and the like. To solve the above problems, the present invention is realized by:
the preparation method of the fluorine intercalated graphitized carbon material can be implemented according to the following steps:
the preparation method of the fluorine intercalation graphitized carbon material can be implemented according to the following steps:
(1) Mixing an amino compound and a layered compound, heating to 200-400 ℃ by a program, keeping the temperature for a plurality of hours at a constant temperature, and slowly cooling to room temperature to obtain a thermal intercalation precursor material;
(2) Stirring the thermal intercalation precursor material in the step (1) and an organic solvent for reaction, washing and drying the solid, heating the solid to 600-850 ℃ in an air atmosphere, keeping the temperature for a plurality of hours, and slowly cooling the solid to room temperature;
(3) And (3) reacting the product obtained in the step (2) with a fluorine-containing strong acid mixed solution, centrifugally separating a residual solution, adding a washing solution, washing for a plurality of times, and drying in vacuum to obtain the target product.
As a preferable scheme, in the step (1) of the invention, the amino compound and the layered compound are uniformly mixed and then placed in a corundum quartz boat, heated to 200-400 ℃ at the speed of 5-8 ℃/min under the air atmosphere, kept at the constant temperature of 2-4 h, and then slowly cooled to the room temperature.
Further, in the step (2), the hot-plug layer precursor and 15-40 mL organic solvent are stirred and reacted for 3-60 h at 40-90 ℃, and the hot-plug layer precursor is dried at 40-80 ℃ after being washed by 100-200 ml deionized water; heating to 600-850 deg.c in air, maintaining at 1-4 h, and cooling slowly to room temperature.
Further, in the step (3), the obtained product reacts with the fluorine-containing strong acid mixed solution at the temperature of 40-60 ℃ for 1-20 h, and the residual liquid is dried at the temperature of 40-80 ℃ after being washed by the deionized water and ethanol mixed solution.
In step (1), the amino compound is one or a mixture of two or more of cyanamide, dicyandiamide, urea and thiourea.
Further, in the step (1) of the present invention, the layered compound is one or a mixture of more than two of hydrotalcite, granite, and montmorillonite.
Furthermore, the mass ratio of the amino compound to the layered compound is 1:3-20.
Further, in the step (2) of the present invention, the organic solvent is one or a mixture of two or more of formaldehyde, ethanol, isopropanol, acetaldehyde and phosphoric acid.
Furthermore, the heating rate of the invention in air is 1-10 ℃/min.
Further, in the step (3), the fluorine-containing strong acid solution is one or a mixture of two or more of hydrochloric acid, sulfuric acid organic fluoric acid and inorganic fluoric acid; the rotational speed of centrifugal separation is kept between 8000 and 10000 r/min.
Compared with the prior art, the invention has the following beneficial effects.
(1) The preparation of the fluorine ion intercalation graphitized carbon material is realized by a simple fluorine-containing strong acid soaking mode.
(2) The material synthesized by the invention has wide raw material source and low cost, and is beneficial to large-scale production and application.
(3) Fluorine ions are embedded between the six-membered ring framework layers of the graphitized carbon, so that the lithium adsorption capacity of the graphitized carbon is improved, and the lithium storage performance of the material is improved.
(4) The template etching process of the fluorine-containing strong acid generates a thin amorphous carbon structure on the surface of the graphitized carbon material, so that the conductivity of the material is increased, and the cycle stability of the lithium battery negative electrode material is effectively improved.
Drawings
The invention is further described with reference to the following figures and detailed description. The scope of the invention is not limited to the following expressions.
FIG. 1 is an XRD pattern of a composite material obtained in example 1 of the present invention;
FIG. 2 is a TEM image of a composite material obtained in example 2 of the present invention;
FIG. 3a is a drawing showing nitrogen adsorption stripping of the composite material obtained in example 3 of the present invention; FIG. 3b is a graph of the aperture distribution;
FIG. 4 is a graph showing the charge and discharge performance of the composite material obtained in example 4 of the present invention.
Detailed Description
Example 1
(1) Weighing 3 g dicyandiamide and 15 g magnesium aluminum hydrotalcite, fully and uniformly mixing, putting the mixed sample into a 200 ml crucible, heating to 310 ℃ at 8 ℃/min in an air atmosphere, keeping the temperature at constant temperature of 2.5 h, and slowly cooling to room temperature to obtain the dicyandiamide hot intercalation precursor compound. And (3) carrying out uniform stirring reaction on the dicyandiamide hot intercalation precursor compound and 20 mL isopropanol hot solution at 50 ℃ at a stirring speed of 150 r/min for 3.5 h, carrying out suction filtration and washing, and drying at a constant temperature of 80 ℃ for 12 h. The resulting material was rapidly heated to 690 ℃ at a heating rate of 7 ℃/min in an air atmosphere and held at constant temperature for 3 hours, followed by slow cooling to room temperature.
(2) Uniformly mixing a sample after high-temperature roasting in a mixed solution of 300 ml dilute nitric acid, hydrochloric acid and hydrofluoric acid (1. The X-ray diffraction pattern of the prepared material is shown in the following figure.
Example 2
(1) Weighing 2 g thiourea and granite, uniformly mixing the thiourea and the granite according to the mass ratio of 1:6, putting the mixture into a crucible, heating the mixture to 250 ℃ at the speed of 5 ℃/min in the air, maintaining the temperature of 3.5 h, and slowly cooling the mixture to the room temperature to obtain the thiourea intercalated precursor material. The thiourea intercalated precursor material and 120 mL ethanol solution are stirred to react at 40 ℃ for 8 h, and after the steps of suction filtration, washing, drying and the like, 12 h is dried at 60 ℃. Heating to 620 ℃ at 7 ℃/min in air, keeping 2 h at constant temperature, and then rapidly cooling to room temperature.
(2) And (3) placing the roasted sample in a mixed solution of organic fluorine-containing strong acid and dilute nitric acid, performing thermal reflux reaction at 70 ℃ for 6 h, washing the product with deionized water and absolute ethyl alcohol for several times respectively, and performing vacuum drying at 60-80 ℃. And obtaining the fluorine intercalation graphitized carbon nano-mesh composite material. The nano sheet material prepared has an amorphous carbon layer structure as shown in fig. 2.
Example 3
(1) Weighing 5g of urea and montmorillonite, uniformly mixing the urea and the montmorillonite according to the mass ratio of 1:3, putting the mixture into a quartz boat, heating the mixture to 340 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping the temperature at constant temperature for 2.5 h, and then rapidly cooling the mixture to the room temperature to obtain the urea intercalation precursor material. Slowly stirring the urea intercalation precursor material and a mixed solution of 130 mL acetaldehyde and formaldehyde at 40 ℃ for 3h, performing suction filtration and washing, and drying 12 h at 80 ℃. The dried sample is put into a ceramic crucible and heated to 820 ℃ at the speed of 5 ℃/min, and is slowly cooled to room temperature after being kept at the constant temperature of 1.5 h.
(2) And (2) slowly stirring the roasted sample and a mixed solution of organic fluorine-containing strong acid and dilute sulfuric acid at 40 ℃ to react for 3.5 h, centrifugally separating residual liquid at a constant rotating speed of 9000r/min, washing the obtained solid material for multiple times by using mixed washing liquid, and drying in vacuum at 70 ℃ to obtain the fluorine intercalation graphitized carbon nanosphere composite material. As shown in fig. 3, the prepared material has a large specific surface area and a pore structure.
Example 4
(1) Weighing 4g of cyanamide and nickel iron hydrotalcite, uniformly mixing the samples according to the mass ratio of the cyanamide to the nickel iron hydrotalcite of 1:4, putting the mixture into a corundum quartz boat, rapidly heating the mixture to 260 ℃ in air at the heating rate of 6 ℃/min, keeping the temperature at 3h, and slowly cooling the mixture to room temperature to obtain a precursor compound of the cyanamide thermal intercalation nickel iron hydrotalcite. Slowly stirring a precursor compound of the cyanamide hot-insert-layer nickel-iron hydrotalcite and a mixed solution of 25 mL phosphoric acid and acetaldehyde at 45 ℃, keeping 8 h, and drying the mixed solution at 60 ℃ after suction filtration and washing. After being ground, the obtained solid material is heated to 700 ℃ in the air at the heating rate of 2 ℃/min, and slowly cooled to the room temperature after the constant temperature is maintained at 3 h.
(2) And soaking the roasted sample in a mixed solution of organic strong fluorine acid and concentrated hydrochloric acid, performing ultrasonic reaction at 40 ℃, keeping for 20 min, and performing suction filtration, washing, vacuum drying and other steps on the reacted solution to obtain the fluorine intercalation nitrogen and fluorine co-doped carbon nano flaky composite material. Then, a sample of 50 mg is weighed for testing the charge and discharge performance of the lithium ion battery. As shown in fig. 4, the resulting material has good lithium electrical properties.
It is understood that various other changes and modifications may be made by those skilled in the art based on the technical idea of the present invention, and all such changes and modifications should fall within the protective scope of the claims of the present invention.
Claims (5)
1. The preparation method of the fluorine intercalation graphitized carbon material is characterized by comprising the following steps:
(1) Uniformly mixing an amino compound and a layered compound, placing the mixture in a corundum quartz boat, heating the mixture to 200-400 ℃ at the speed of 5-8 ℃/min under the air atmosphere, keeping the temperature for 2-4 h, and then slowly cooling the mixture to room temperature to obtain a thermal intercalation precursor material; the amino compound is one or a mixture of more than two of cyanamide, dicyandiamide, urea and thiourea; the layered compound is one or a mixture of more than two of hydrotalcite, granite and montmorillonite; the mass ratio of the amino compound to the layered compound is 1:3-20;
(2) Stirring the thermal intercalation precursor material in the step (1) and an organic solvent for reaction, washing and drying the solid, heating to 600-850 ℃ in air atmosphere, keeping the temperature for a plurality of hours, and slowly cooling to room temperature;
(3) And (3) reacting the product obtained in the step (2) with a fluorine-containing strong acid mixed solution at the temperature of 40-75 ℃ for 1-20 h, washing the residual liquid with a deionized water and ethanol mixed solution, and drying at the temperature of 40-80 ℃ to obtain the target product.
2. The method according to claim 1, wherein the step of preparing the fluorine intercalated graphitized carbon material comprises: in the step (2), the hot-plug layer precursor and 15-40 mL organic solvent are stirred to react at 40-90 ℃ for 2-60 h, and the mixture is washed by 100-200 ml deionized water and then dried at 40-80 ℃; heating to 600-850 deg.C in air, keeping at 1-4 h, and slowly cooling to room temperature.
3. The method for preparing a fluorine intercalated graphitized carbon material as claimed in claim 2, wherein: in the step (2), the organic solvent is one or a mixture of more than two of formaldehyde, ethanol, isopropanol, acetaldehyde and phosphoric acid.
4. The method according to claim 3, wherein the step of preparing the fluorine-intercalated graphitized carbon material comprises: the heating rate in the air is 1-10 ℃/min.
5. The method according to claim 4, wherein the step of preparing the fluorine intercalated graphitized carbon material comprises: in the step (3), the strong fluorine-containing acid in the strong fluorine-containing acid mixed solution is strong organic or strong inorganic fluorine-containing acid; the rotational speed of centrifugal separation is kept between 8000 and 10000 r/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103130215A (en) * | 2013-03-05 | 2013-06-05 | 电子科技大学 | Silicon surface SiC epitaxial graphene liquid phase fluorine intercalation method |
| CN104733716A (en) * | 2014-12-04 | 2015-06-24 | 辽宁石油化工大学 | Molybdenum oxide/nitrogen-doped carbon composite electrode material and preparation method thereof |
| CN109772419A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space |
| CN110600713A (en) * | 2019-10-09 | 2019-12-20 | 中国科学技术大学 | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery |
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| CN1326267C (en) * | 2005-05-27 | 2007-07-11 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130215A (en) * | 2013-03-05 | 2013-06-05 | 电子科技大学 | Silicon surface SiC epitaxial graphene liquid phase fluorine intercalation method |
| CN104733716A (en) * | 2014-12-04 | 2015-06-24 | 辽宁石油化工大学 | Molybdenum oxide/nitrogen-doped carbon composite electrode material and preparation method thereof |
| CN109772419A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space |
| CN110600713A (en) * | 2019-10-09 | 2019-12-20 | 中国科学技术大学 | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery |
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