CN111392723A - Preparation method of porous graphite, product and application thereof - Google Patents
Preparation method of porous graphite, product and application thereof Download PDFInfo
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- CN111392723A CN111392723A CN202010224700.4A CN202010224700A CN111392723A CN 111392723 A CN111392723 A CN 111392723A CN 202010224700 A CN202010224700 A CN 202010224700A CN 111392723 A CN111392723 A CN 111392723A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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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
- 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
- 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
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of porous graphite, which comprises the following steps: placing the graphite raw material in corrosive gas for heat treatment to obtain porous graphite; the corrosive gas is selected from carbon dioxide, air or an oxygen-containing atmosphere. The invention discloses a preparation method of porous graphite, which only comprises a one-step heat treatment process, does not need any post-treatment, is simple and controllable and is convenient for industrial production. The prepared porous graphite has a large specific surface area and can be used as a lithium ion battery negative electrode material capable of being quickly charged.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a preparation method of porous graphite, a product and application thereof.
Background
Lithium ion batteries (L IBs) have high specific capacity, long service life, environmental protection and other advantages, and are widely used in daily life, such as household appliances, electric vehicles and the like, however, the currently used lithium ion batteries have limited capacity and are difficult to meet the increasing demand.
Chinese patent document with application publication No. CN 107305949a discloses a porous graphite negative electrode material, and a preparation method and an application thereof, wherein the preparation method of the porous graphite negative electrode material comprises the following steps: uniformly loading metal and/or a compound containing a metal element on the surface of graphite to form a composite; heat treating the composite in an oxygen-containing atmosphere to form a porous graphite material; and removing the metal and/or the compound containing the metal element remaining in the porous graphite material to obtain a porous graphite anode material. The preparation process needs to load metal or metal compound on the surface of graphite, remove metal elements by acid cleaning after etching, is complex, is easy to introduce metal impurities, and reduces the purity of graphite. In addition, the process etches the metal and the metal compound only on the layered surface and the end face of the graphite to obtain the void, but the specific surface area of the prepared porous graphite is only 8m at most2/g。
Chinese patent publication No. CN 107758655 a discloses porous graphite, and a preparation method and application thereof. The method comprises the following steps: (1) calcining ferrous gluconate at 700-1000 ℃ for 2-5 h in an inert atmosphere to obtain carbide powder; (2) soaking carbide powder in hydrochloric acid with the mass fraction of 20-38% for 2-5 h to remove iron-containing impurities, performing suction filtration by using a microporous filter membrane in a vacuum state, and washing with deionized water to be neutral; (3) and (3) repeating the step (2) for 1-2 times to ensure that the iron-containing impurities are completely removed, and drying to obtain the porous graphite. The preparation process also needs to introduce metal firstly and then remove the metal, and has complex process, easy introduction of metal impurities and reduction of the purity of graphite.
Poplar scholar et al (a spherical artificial porous graphite cathode material and a preparation method thereof; university of three gorges; 2015) prepared porous graphite by a bottom-up method, and basically prepared the following steps: (1) the anthracite particles are thinned to be below 0.5 micron by a ball milling method; (2) acid washing and purifying the finely ground anthracite; (3) the purified anthracite particles are pulped and then spray dried to obtain spherical anthracite particles; (4) the spherical artificial porous graphite cathode material is obtained by high-temperature heat treatment of the anthracite particles under nitrogen. The method for carrying out the early granulation and the final graphitization by the anthracite raw material has complex process and is difficult to realize large-scale preparation.
Disclosure of Invention
Aiming at the problems, the invention discloses a preparation method of porous graphite, which only comprises a one-step heat treatment process, does not need any post-treatment, is simple and controllable and is convenient for industrial production. The prepared porous graphite has a large specific surface area and can be used as a lithium ion battery negative electrode material capable of being quickly charged.
The specific technical scheme is as follows:
placing the graphite raw material in corrosive gas for heat treatment to obtain the porous graphite;
the corrosive gas is selected from carbon dioxide, air or an oxygen-containing atmosphere.
The invention firstly provides a method for obtaining internal pores by reacting corrosive gas with active points in graphite at high temperature, and finally the porous graphite material with high specific surface area is prepared. The preparation method only has one step, does not need early pretreatment or subsequent post-treatment, is simple and controllable, and is suitable for large-scale industrial production.
Preferably, the graphite raw material is selected from at least one of artificial graphite, natural graphite and mesocarbon microbeads.
Preferably, the particle size D50 of the graphite raw material is 2-25 μm; more preferably 15 μm. Tests show that the porous graphite prepared by using the graphite raw material with the preferred particle size has higher specific surface area.
The invention discloses three kinds of corrosive gases, and the heat treatment temperature is respectively optimized aiming at different corrosive gases.
When the corrosive gas is selected from carbon dioxide, the heat treatment temperature is 1000-1200 ℃, and tests show that the heat treatment temperature is too low, such as 800 ℃, the product does not obtain a porous structure, and the specific surface area is low; the heat treatment temperature is too high, such as 1400 ℃, the corrosion of the product is serious, and the specific surface area is still very low.
The heat treatment time is 0.5-20 h, the reaction time is too short, and the corrosion effect is poor; and the time is too long, most of graphite is corroded, and the yield is too low. Generally, as the heat treatment temperature increases, the heat treatment time is shortened accordingly.
When the corrosive gas is selected from air, the heat treatment temperature is 450-600 ℃, the heat treatment temperature is too low, and the product does not obtain a porous structure; the heat treatment temperature is too high, and the corrosion of products is serious; in both cases, porous graphite having a high specific surface area cannot be obtained.
The heat treatment time is 0.5-20 h, and generally, the heat treatment time is correspondingly shortened along with the increase of the heat treatment temperature.
In the present invention, the oxygen-containing atmosphere comprises oxygen and an inert gas; preferably, when the corrosive gas is selected from an oxygen-containing atmosphere, the heat treatment temperature is 400-800 ℃, the heat treatment temperature is too low, and the product does not obtain a porous structure; the heat treatment temperature is too high, and the corrosion of products is serious; in both cases, porous graphite having a high specific surface area cannot be obtained.
Tests show that when the volume fraction of oxygen exceeds 25%, under the conventional heat treatment temperature (400-800 ℃), the product is seriously corroded due to the over-high corrosion rate; when the heat treatment temperature is continuously reduced, the chemical reaction between the graphite and the oxygen can not be carried out, and the corrosion effect can not be achieved. When the volume fraction of oxygen is less than 5%, the consumption of other gases is large, which is not favorable for controlling the cost in large-scale production. Therefore, the volume fraction of oxygen in the oxygen-containing atmosphere is further preferably 5% to 25% based on a combination of economic factors and product properties.
The heat treatment temperature is ensured to be within the range (400-800 ℃) and can be adjusted according to the content adjustment of the oxygen, and generally, the heat treatment temperature is correspondingly reduced along with the increase of the content of the oxygen.
The heat treatment time is 0.5-20 h, and generally, the heat treatment time is correspondingly shortened along with the increase of the heat treatment temperature.
Further preferably, the corrosive gas is selected from carbon dioxide, and tests show that when carbon dioxide is used as the corrosive gas, the reaction activity of carbon dioxide and graphite is lower, the progress of the corrosion reaction is easier to control, and therefore, the specific surface area of the final product is easier to control through the control of the reaction time or temperature, and porous graphite with better performance is obtained.
The invention also discloses the porous graphite prepared by the process. The specific surface area of the product is over 150m2And the interior of the material has pores with nanoscale and microscale simultaneously, and the material can be used as a battery cathode material to be applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for preparing porous graphite by a one-step method, which only takes graphite as a raw material, utilizes corrosive gas to react with active points in the graphite at high temperature to obtain internal pores, does not introduce any impurity, has high product purity and does not need post-treatment.
The porous graphite prepared by the method has high specific surface area and abundant pore structures.
Drawings
FIG. 1 is an SEM image of porous graphite prepared in example 1;
FIG. 2 is a pore size distribution curve of porous graphite prepared in example 1;
FIG. 3 is an SEM photograph of the final product prepared in comparative example 1;
FIG. 4 is an SEM photograph of the final product prepared in comparative example 2;
FIG. 5 SEM image of porous graphite prepared in example 5;
FIG. 6 is a pore size distribution curve of porous graphite prepared in example 5;
FIG. 7 SEM image of porous graphite prepared in example 6;
fig. 8 is a pore size distribution curve of the porous graphite prepared in example 6.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
2g of natural graphite (the granularity D50 is 15.4 mu m) is taken as a raw material and placed in a corundum boat, the corundum boat is placed in a tube furnace for heat treatment, the heating rate is 10 ℃/min, the reaction temperature is 1100 ℃, and the reaction time is 6 hours, so that the final product is obtained.
An SEM picture of the porous graphite prepared in this example is given in fig. 1, and it can be seen from observing fig. 1 that the graphite exhibits a porous structure.
Fig. 2 shows the pore size distribution curve of the porous graphite prepared in this example, and the porous graphite prepared in this example has an average pore size of 249.8nm, which was measured three times.
The specific surface area of the porous graphite prepared in the example was 220.4m2/g。
Comparative example 1
The preparation process is exactly the same as in example 1, except that the reaction temperature is replaced by 800 ℃.
Fig. 3 is an SEM picture of the final product prepared in the present comparative example, and it can be seen that the pore size of the product was not observed.
The product prepared in this comparative example was tested to have a specific surface area of 1.1m2/g。
Comparative example 2
The preparation process is exactly the same as in example 1, except that the reaction temperature is replaced by 1400 ℃.
Fig. 4 is an SEM picture of the final product prepared in the present comparative example, and it can be seen that the product is severely corroded.
The product prepared in this comparative example was tested to have a specific surface area of 11.1m2/g。
Examples 2 to 3
The preparation process was exactly the same as in example 1, except that the reaction temperature was replaced with 1000 ℃ and 1200 ℃ respectively.
Through observation, the products respectively prepared all present porous structures. The specific surface area was tested to be comparable to example 1.
Example 4
The preparation process was exactly the same as in example 1, except that the particle size D50 of the natural graphite was 21.2 μm.
The product was observed to exhibit a porous structure. The specific surface area is tested to be 152.6m2/g。
Example 5
The preparation process was exactly the same as in example 1, except that the etching gas was replaced with air and the reaction temperature was replaced with 500 ℃.
An SEM picture of the porous graphite prepared in this example is given in fig. 5, and it can be seen from observing fig. 5 that the graphite exhibits a porous structure.
Fig. 6 shows a pore size distribution curve of the porous graphite prepared in this example, and the porous graphite prepared in this example has an average pore size of 105.3nm, which was measured three times.
Comparative example 3
The preparation process is exactly the same as in example 5, except that the reaction temperature is replaced by 800 ℃.
When the SEM image is observed, the reactants are completely reacted, and the final product cannot be obtained.
Example 6
The preparation process is exactly the same as in example 1, except that the etching gas is replaced by a mixed gas of oxygen and nitrogen with 10% by volume of oxygen, and the reaction temperature is replaced by 600 ℃.
An SEM picture of the porous graphite prepared in this example is shown in fig. 7, and it can be seen from the observation of fig. 7 that the graphite exhibits a porous structure.
Fig. 8 shows a pore size distribution curve of the porous graphite prepared in this example, and the porous graphite prepared in this example has an average pore size of 92.8nm, which was measured three times.
Example 7
The preparation process was exactly the same as in example 6, except that the volume fraction of oxygen in the oxygen-containing atmosphere was replaced with 25% and the reaction temperature was replaced with 400 ℃.
Observing the SEM image, the product presents a porous structure.
Example 8
The preparation process was exactly the same as in example 6, except that the volume fraction of oxygen in the oxygen-containing atmosphere was replaced with 5% and the reaction temperature was replaced with 800 ℃.
Observing the SEM image, the product presents a porous structure.
Comparative example 4
The preparation process was exactly the same as in example 6, except that the volume fraction of oxygen in the oxygen-containing atmosphere was replaced with 40%.
When the SEM image is observed, the reactants are completely reacted, and the final product cannot be obtained.
Claims (10)
1. A method for preparing porous graphite, comprising:
placing the graphite raw material in corrosive gas for heat treatment to obtain the porous graphite;
the corrosive gas is selected from carbon dioxide, air or an oxygen-containing atmosphere.
2. The method for preparing porous graphite according to claim 1, wherein the graphite raw material is at least one selected from the group consisting of artificial graphite, natural graphite, and mesocarbon microbeads.
3. The method for preparing porous graphite according to claim 2, wherein the particle size D50 of the graphite raw material is 2 to 25 μm.
4. The method of preparing porous graphite according to claim 1, wherein the oxygen-containing atmosphere comprises oxygen and an inert gas.
5. The method of claim 4, wherein the volume fraction of oxygen in the oxygen-containing atmosphere is 5 to 25%.
6. The method for preparing porous graphite according to claim 1, characterized in that:
the corrosive gas is selected from carbon dioxide, the heat treatment temperature is 1000-1200 ℃, and the time is 0.5-20 h.
7. The method for preparing porous graphite according to claim 1, characterized in that:
the corrosive gas is selected from air, the heat treatment temperature is 450-600 ℃, and the time is 0.5-20 hours.
8. The method for preparing porous graphite according to claim 1, characterized in that:
the corrosive gas is selected from oxygen-containing atmosphere, the heat treatment temperature is 400-800 ℃, and the time is 0.5-20 h.
9. Porous graphite prepared according to the method of any one of claims 1 to 8.
10. Use of the porous graphite of claim 9 in a lithium ion battery.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112366299A (en) * | 2020-10-28 | 2021-02-12 | 浙江大学 | Preparation method of graphite-silicon-based lithium ion battery negative electrode material and product thereof |
CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
CN114068885A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Graphite material with porous carbon layer and preparation method and application thereof |
CN114188533A (en) * | 2021-12-20 | 2022-03-15 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
CN114242978A (en) * | 2021-12-14 | 2022-03-25 | 梅州市量能新能源科技有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
CN114477158A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | C-axis pore-forming graphite and preparation method and application thereof |
CN114477160A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | Method for preparing high-purity porous graphite |
CN115215335A (en) * | 2022-08-31 | 2022-10-21 | 浙江碳一新能源有限责任公司 | Modified graphite and preparation method and application thereof |
WO2023133662A1 (en) * | 2022-01-11 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Modified graphite and preparation method therefor, carbon-coated negative electrode active material and preparation method therefor, negative electrode piece, secondary battery, battery module, battery pack, and electric device |
CN116979053A (en) * | 2023-06-30 | 2023-10-31 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103303907A (en) * | 2013-04-28 | 2013-09-18 | 南昌大学 | Surface modification method for spherical graphite negative material |
-
2020
- 2020-03-26 CN CN202010224700.4A patent/CN111392723A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103303907A (en) * | 2013-04-28 | 2013-09-18 | 南昌大学 | Surface modification method for spherical graphite negative material |
Non-Patent Citations (4)
Title |
---|
LUO XIAOWEI,等: "Effect of temperature on graphite oxidation behavior", 《NUCLEAR ENGINEERING AND DESIGN》 * |
YUN-SOO LIM,等: "Change of properties after oxidation of IG-11 graphite by air and CO2 gas", 《JOURNAL OF NUCLEAR MATERIALS》 * |
吴宇平,等: "锂离子电池负极材料的制备", 《电池》 * |
黄振兴,等: "《活性炭技术基础》", 30 June 2006 * |
Cited By (11)
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CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
CN114068885A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Graphite material with porous carbon layer and preparation method and application thereof |
CN114477158A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | C-axis pore-forming graphite and preparation method and application thereof |
CN114477160A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | Method for preparing high-purity porous graphite |
CN114477158B (en) * | 2020-10-27 | 2023-08-04 | 武汉大学 | C-axis pore-forming graphite and preparation method and application thereof |
CN112366299A (en) * | 2020-10-28 | 2021-02-12 | 浙江大学 | Preparation method of graphite-silicon-based lithium ion battery negative electrode material and product thereof |
CN114242978A (en) * | 2021-12-14 | 2022-03-25 | 梅州市量能新能源科技有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
CN114188533A (en) * | 2021-12-20 | 2022-03-15 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
WO2023133662A1 (en) * | 2022-01-11 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Modified graphite and preparation method therefor, carbon-coated negative electrode active material and preparation method therefor, negative electrode piece, secondary battery, battery module, battery pack, and electric device |
CN115215335A (en) * | 2022-08-31 | 2022-10-21 | 浙江碳一新能源有限责任公司 | Modified graphite and preparation method and application thereof |
CN116979053A (en) * | 2023-06-30 | 2023-10-31 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
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