CN115806291A - Graphite negative electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Graphite negative electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN115806291A CN115806291A CN202211691961.2A CN202211691961A CN115806291A CN 115806291 A CN115806291 A CN 115806291A CN 202211691961 A CN202211691961 A CN 202211691961A CN 115806291 A CN115806291 A CN 115806291A
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- electrode material
- negative electrode
- graphite
- boron
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 46
- 239000010439 graphite Substances 0.000 title claims abstract description 46
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000010406 cathode material Substances 0.000 claims abstract description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- 238000005087 graphitization Methods 0.000 claims abstract description 20
- 239000000571 coke Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- -1 saccharide compound Chemical class 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 13
- 238000001237 Raman spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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 graphite cathode material, a preparation method and application thereof and a lithium ion battery. The preparation method of the graphite negative electrode material comprises the following steps: mixing spherical coke particles with a boron source, and carrying out graphitization treatment to obtain the graphite cathode material; wherein, the boron element in the boron source accounts for 0.5 to 10 percent of the mass of the spherical coke particles. The graphite cathode material prepared by the method has small particle size, regular shape, spherical shape and high graphitization degree; the graphite cathode material prepared by the invention has the advantage of excellent electrochemical performance when used for preparing a lithium ion battery, and can improve the quick charge performance.
Description
Technical Field
The invention particularly relates to a graphite cathode material, a preparation method and application thereof and a lithium ion battery.
Background
With the vigorous development of consumer electronics and electric vehicles, increasingly strict requirements are put forward on the rapid charging technology, the rate capability of the lithium battery of consumer electronics in the current market reaches 10C, and the electric vehicle gradually develops to 6C, so that from the viewpoint of material design, a new material needs to be designed to support the development of the rapid charging technology. During the rapid charging of the battery, if the kinetics of the negative electrode material is insufficient, lithium may precipitate, resulting in degradation of the overall cycle performance of the battery. Therefore, the insufficient dynamics of the negative electrode material is a key difficulty for restricting the development of the rapid charging technology. At present, a key method for improving the dynamic performance of the graphite negative electrode material is to reduce the particle size of particles and reduce the transmission distance of lithium ions in the particles.
Currently, petroleum coke is basically used as a raw material for manufacturing the conventional artificial graphite cathode material, the particle size of a crushed product of the artificial graphite cathode material is limited to processing equipment, the particle size can only be controlled to be about 5 micrometers, and the geometric shape of the crushed product is irregular. The problem of uneven stress distribution of graphite particles with irregular shapes in the process of quick charging and quick discharging cyclic expansion and contraction easily causes mechanical damage of the particles, and is not beneficial to circulation. Therefore, the significance of developing the graphite cathode material which can reduce the particle size, improve the geometric shape and obtain larger graphitization degree is remarkable.
Disclosure of Invention
The invention aims to overcome the defects of large particle size, irregular shape and difficult graphitization of a graphite cathode material in the prior art, and provides the graphite cathode material, a preparation method and application thereof and a lithium ion battery. The graphite cathode material prepared by the method has small particle size, regular shape, spherical shape and high graphitization degree; the graphite cathode material prepared by the invention has the advantage of excellent electrochemical performance when used for preparing a lithium ion battery, and can improve the quick charge performance.
The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a graphite cathode material, which comprises the following steps:
mixing spherical coke particles with a boron source, and carrying out graphitization treatment to obtain the graphite cathode material;
wherein, the boron element in the boron source accounts for 0.5 to 10 percent of the mass percentage of the spherical coke particles.
In the present invention, the spherical coke particles preferably have a particle diameter of 100nm to 10 μm.
In the present invention, the temperature of the graphitization treatment may be 2900 to 3200 ℃, for example, 3000 ℃.
In the present invention, the time for the graphitization treatment may be 12 to 36 hours, for example, 15 hours, 20 hours, or 25 hours.
In the present invention, the equipment for the graphitization treatment may be conventional in the art, such as a graphitization furnace.
In the present invention, the atmosphere of the graphitization treatment is preferably an argon atmosphere.
In the present invention, the method for preparing the shot coke particles comprises the steps of: the carbohydrate is subjected to hydrothermal reaction to obtain spherical coke particles.
Wherein, the saccharide compound can be conventional in the art, and is preferably sucrose, glucose or lactose.
Wherein the temperature of the hydrothermal reaction can be 160-200 ℃, for example 190 ℃.
Wherein, the time of the hydrothermal reaction can be 6 to 20 hours, such as 10 hours.
Wherein, after the hydrothermal reaction is finished, washing and drying operations are preferably carried out.
The washing may be conventional in the art, for example with a suction filtration wash with deionized water.
The number of washes may be conventional in the art, e.g., 3.
The drying may be conventional in the art, such as oven drying.
In the present invention, the graphitization treatment is preferably followed by mixing and sieving.
In the present invention, the boron source may be a boron-containing compound conventional in the art, preferably boric acid or boron carbide.
In the present invention, the content of boron in the boron source is preferably 0.5% to 9%, for example, 3% by mass of the shot coke particles.
In the present invention, the particle size of the graphite negative electrode material is preferably 100 to 1000nm.
In the present invention, the graphite negative electrode material preferably further contains boron, preferably in the form of boron-carbon solid solution.
In the invention, the boron element in the graphite cathode material accounts for 0.5-5% of the graphite cathode material by mass.
The invention also provides the graphite cathode material prepared by the preparation method.
The invention also provides application of the graphite negative electrode material as an electrode material in a lithium ion battery.
The electrode material is preferably a negative electrode material.
The invention also provides a lithium ion battery which comprises the graphite cathode material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the invention starts from nano-scale spherical coke particles with small particle size, and the nano-scale spherical coke particles are mixed with a boron source and then are subjected to catalytic graphitization and high-temperature graphitization treatment to prepare the graphite cathode material which has both spherical geometric shape and small particle size and high graphitization degree, so that the quick charging performance of the material is further improved; the graphite cathode material prepared by the invention has the advantage of excellent electrochemical performance when used for preparing a lithium ion battery.
Drawings
Fig. 1a is a raman spectrum of the graphite anode material prepared in example 1; fig. 1b is a raman spectrum of the hard carbon material prepared in comparative example 1.
Fig. 2 is a scanning electron microscope image of the graphite negative electrode material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Stirring and dissolving 50g of sucrose by using 500mL of deionized water, placing the mixture into a polytetrafluoroethylene lining of a 500mL hydrothermal reaction kettle, assembling the hydrothermal reaction kettle, heating to 190 ℃, heating at a constant temperature for 10 hours, opening the hydrothermal reaction kettle when the temperature is reduced to room temperature, taking out the material A, performing suction filtration, cleaning and suction filtration for 3 times by using the deionized water, and drying to obtain a material B, wherein the particle size is represented by a scanning electron microscope to be between 100nm and 10 mu m.
(2) And mixing the material B with boric acid, wherein the boric acid contains 3% of boron element in the material B by mass. Placing the mixture in a small-sized graphitization furnace, carrying out programmed heating to 3000 ℃ in an argon atmosphere, keeping for 12h, taking out after cooling to obtain a material C, and mixing and screening to obtain a material D with the particle size of 100-1000 nm.
Comparative example 1
(1) Stirring and dissolving 50g of sucrose by using 500mL of deionized water, placing the mixture into a polytetrafluoroethylene lining of a 500mL hydrothermal reaction kettle, assembling the hydrothermal reaction kettle, heating to 190 ℃, heating at a constant temperature for 10 hours, opening the hydrothermal reaction kettle when the temperature is reduced to room temperature, taking out the material A, performing suction filtration, cleaning and suction filtration for 3 times by using the deionized water, and drying to obtain a material B, wherein the particle size is represented by 100nm to 10 mu m through a scanning electron microscope.
(2) And placing the material B in a nitrogen atmosphere muffle furnace, and calcining at the high temperature of 1200 ℃ for 10h for carbonization to form the hard carbon material.
Effect example 1
1. Raman spectrum
The raman spectrum of the graphite cathode material prepared in example 1 of the present invention is shown in fig. 1, and fig. 1a is the raman spectrum of the graphite cathode material prepared in example 1; fig. 1b is a raman spectrum of the hard carbon material prepared in comparative example 1. Comparing the two, it can be found that the graphite anode material shows a narrower G peak, and is significantly different from the hard carbon material, indicating that it is a graphitized material.
2、SEM
The scanning electron microscope image of the graphite cathode material prepared in example 1 of the present invention is shown in fig. 2, and it can be seen from fig. 2 that the graphite cathode material has uniform particle size, mainly ranging from 100nm to 1000nm, and the form is spherical.
3. Electrical Performance testing
(1) The graphite negative electrode material prepared in example 1, super P (conductive agent), CMC (sodium carboxymethyl cellulose) and SBR (poly styrene butadiene rubber) are mixed with water and stirred uniformly to form slurry, the slurry is coated on the surface of a copper foil current collector, after vacuum drying is carried out for 24 hours, a pole piece is rolled, and then the round pole piece is formed by die cutting.
(2) And manufacturing the pole piece, the diaphragm, the lithium piece and the electrolyte into a button cell for testing.
(3) The prepared button cell is arranged on a test cabinet for detection, the current density is 20mA/g, the charging and discharging upper and lower limit potentials are 1.5V-0.005V, and the test capacity is 300mAh/g.
Claims (10)
1. The preparation method of the graphite negative electrode material is characterized by comprising the following steps of:
mixing spherical coke particles with a boron source, and carrying out graphitization treatment to obtain the graphite cathode material;
wherein, the boron element in the boron source accounts for 0.5 to 10 percent of the mass percentage of the spherical coke particles.
2. The method for preparing a graphite negative electrode material according to claim 1, wherein the spherical coke particles have a particle diameter of 100nm to 10 μm;
and/or the boron element in the boron source accounts for 0.5-9 percent, such as 3 percent, of the mass of the spherical coke particles.
3. The method for preparing a graphite negative electrode material according to claim 1, wherein the graphitization treatment satisfies one or more of the following conditions:
(1) The temperature of the graphitization treatment is 2900-3200 ℃, such as 3000 ℃;
(2) The graphitization treatment time is 12-36 h, such as 15h, 20h or 25h;
(3) The graphitizing treatment atmosphere is an argon atmosphere.
4. The method for preparing a graphitic negative electrode material according to claim 1, characterized in that the method for preparing the shot coke particles comprises the following steps: and (3) carrying out hydrothermal reaction on the carbohydrate to obtain spherical coke particles.
5. The method for preparing a graphitic negative electrode material according to claim 4, characterized in that the method for preparing the spherical coke particles satisfies one or more of the following conditions:
(1) The saccharide compound is sucrose, glucose or lactose;
(2) The temperature of the hydrothermal reaction is 160-200 ℃, for example 190 ℃;
(3) The hydrothermal reaction time is 6 to 20 hours, for example 10 hours.
6. The method for preparing a graphite anode material according to claim 1, wherein the boron source is boric acid or boron carbide.
7. The method for preparing a graphitic negative-electrode material according to claim 1, characterized in that it satisfies one or more of the following conditions:
(1) The particle size of the graphite negative electrode material is 100-1000 nm;
(2) Boron exists in the graphite cathode material, and exists in the form of boron-carbon solid solution;
(3) The boron element in the graphite negative electrode material accounts for 0.5-5% of the mass of the graphite negative electrode material.
8. A graphite negative electrode material, characterized in that it is produced by the method for producing a graphite negative electrode material according to any one of claims 1 to 7.
9. Use of the graphite negative electrode material of claim 8 as an electrode material in a lithium ion battery.
10. A lithium ion battery comprising the graphitic negative electrode material according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211691961.2A CN115806291A (en) | 2022-12-27 | 2022-12-27 | Graphite negative electrode material, preparation method and application thereof, and lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211691961.2A CN115806291A (en) | 2022-12-27 | 2022-12-27 | Graphite negative electrode material, preparation method and application thereof, and lithium ion battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040091782A1 (en) * | 2001-03-06 | 2004-05-13 | Yoichi Kawano | Graphite material for negative pole of lithium secondary battery, method of manufacturing the graphite material, and lithium secondary battery |
| CN112310362A (en) * | 2019-07-30 | 2021-02-02 | 珠海冠宇电池股份有限公司 | High-capacity fast-charging negative electrode material for lithium ion battery and lithium ion battery |
| JP2021134113A (en) * | 2020-02-26 | 2021-09-13 | 株式会社村田製作所 | Composite carbon material and method for producing the same, negative electrode active material for lithium ion secondary batteries and lithium ion secondary battery |
| CN114275758A (en) * | 2021-11-30 | 2022-04-05 | 浙江大学 | Preparation method and application of microporous carbon material |
-
2022
- 2022-12-27 CN CN202211691961.2A patent/CN115806291A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040091782A1 (en) * | 2001-03-06 | 2004-05-13 | Yoichi Kawano | Graphite material for negative pole of lithium secondary battery, method of manufacturing the graphite material, and lithium secondary battery |
| CN112310362A (en) * | 2019-07-30 | 2021-02-02 | 珠海冠宇电池股份有限公司 | High-capacity fast-charging negative electrode material for lithium ion battery and lithium ion battery |
| JP2021134113A (en) * | 2020-02-26 | 2021-09-13 | 株式会社村田製作所 | Composite carbon material and method for producing the same, negative electrode active material for lithium ion secondary batteries and lithium ion secondary battery |
| CN114275758A (en) * | 2021-11-30 | 2022-04-05 | 浙江大学 | Preparation method and application of microporous carbon material |
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