CN117682506A - Method for preparing high-performance fluorocarbon battery by taking microporous hard carbon as precursor - Google Patents
Method for preparing high-performance fluorocarbon battery by taking microporous hard carbon as precursor Download PDFInfo
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- CN117682506A CN117682506A CN202211068969.3A CN202211068969A CN117682506A CN 117682506 A CN117682506 A CN 117682506A CN 202211068969 A CN202211068969 A CN 202211068969A CN 117682506 A CN117682506 A CN 117682506A
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- hard carbon
- microporous
- carbon
- precursor
- preparing
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 19
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002243 precursor Substances 0.000 title claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 9
- 238000003682 fluorination reaction Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000143432 Daldinia concentrica Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Abstract
The invention relates to a preparation method of a novel fluorocarbon precursor, in particular to a method for preparing fluorocarbon by using microporous carbon spheres obtained by chemical activation to improve discharge performance of the carbon spheres as a positive electrode material. Firstly preparing phenolic resin by means of prepolymerization, hydrothermal reaction and the like, preparing microporous hard carbon by means of carbonization, KOH activation and the like in sequence, and fluorinating the microporous hard carbon at a certain temperature to obtain carbon fluoride with a microporous structure, wherein the carbon fluoride is applied to a positive electrode material of a primary battery, and the microporous structure is favorable for forming a half-ion C-F bond and improving the multiplying power performance of the primary battery, so that the novel carbon fluoride primary battery with low preparation cost and high energy density is obtained.
Description
Technical Field
The invention relates to a preparation method of a novel fluorocarbon precursor, in particular to a method for preparing a high-performance fluorocarbon battery by forming a micropore structure on the surface of hard carbon through chemical activation and taking a micropore hard carbon material as a precursor. Belongs to the technical field of energy sources.
Background
The energy is the material foundation on which human beings depend to survive, in recent years, the development of science and technology is rapid, the demand of people for energy is more and more, the reserves of fossil energy such as coal, petroleum, natural gas and the like are limited, the long-term energy demand of human beings is difficult to meet, and the requirements of emerging energy such as wind energy, tidal energy and the like on natural conditions are higher, so that the research of the energy storage system has important significance. Electrochemical cells are very important energy storage devices, wherein secondary batteries are widely used in life of people by virtue of rechargeable advantages, but primary batteries are particularly important in special cases such as aerospace, military, field and the like where charging is difficult, and as an important backup energy source, primary batteries must meet the performance requirements of low production cost, high energy density and high-current discharge, and fluorocarbon batteries are widely focused by virtue of high theoretical energy density (2180 Wh/Kg), however, due to poor conductivity of the fluorocarbon itself, the use requirement of high-current discharge is difficult to meet, and the current research of graphene and derivatives thereof as fluorocarbon precursors is more, and the graphene is expensive, so that the wide use of industrialization is difficult to realize, and therefore, a low-cost and excellent-performance fluorocarbon is needed, so that the industrial popularization of the fluorocarbon primary batteries is realized.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance fluorocarbon battery by taking a microporous hard carbon material as a precursor, wherein the microporous structure on the surface is favorable for forming a semi-ion C-F bond, and is more favorable for improving the multiplying power performance of the semi-ion C-F bond compared with a covalent C-F bond, and meanwhile, the super-microporous structure smaller than 0.7nm can enable solvent molecules to enter the inside of a fluorocarbon electrode in the electrochemical reaction process, so that the solvation phenomenon of lithium ions is avoided, and the situations of polarization, heat release and the like of the battery are relieved.
The invention adopts the following technical scheme:
the invention relates to a preparation method of a carbon fluoride anode material, which is characterized by comprising the following steps:
1) Phenol and formaldehyde are used as main reactants, the PH of the solution is regulated to be alkaline, the solution is prepolymerized in a water bath at 60 ℃ for half an hour, and then the phenolic resin microsphere is synthesized through hydrothermal reaction.
2) And carbonizing the phenolic microspheres in a muffle furnace filled with inert gas at 800 ℃ for 2 hours to form the carbon microspheres.
3) Uniformly mixing the carbon microspheres with KOH in a mass ratio of 1:2, and activating the mixture at a high temperature in a muffle furnace filled with inert gas for 1h to obtain the microporous carbon spheres.
4) Placing microporous carbon balls into a fluorination reaction kettle, vacuumizing, and introducing mixed gas (20:80) of fluorine gas and nitrogen gas when the temperature is raised to 200-280 ℃ for reacting for 4 hours to obtain the hard carbon fluoride with a microporous structure.
Preferably, the ratio of the amounts of phenol formaldehyde substances in step 1) is 1:3, the pH of the solution is adjusted to 8, the hydrothermal reaction temperature is 180℃and the reaction time is 12 hours.
Preferably, the activation temperature in step 3) is 700 ℃.
Preferably, the fluorination temperature in step 4) is 250 ℃.
The microporous carbon spheres are prepared by means of hydrothermal reaction, chemical activation and the like. The microporous structure is favorable for the formation of the semi-ionic C-F bond, improves the heat release condition of the battery in the discharging process, and shows excellent discharging performance.
Drawings
FIG. 1 is a scanning electron microscope image of carbon microspheres before and after fluorination according to the present invention;
FIG. 2 is a transmission electron microscope image of carbon microspheres before and after fluorination according to the present invention;
FIG. 3 is a graph showing pore size distribution before and after fluorination in accordance with the present invention;
FIG. 4 is a battery discharge situation of the present invention; (discharge graph of fluorinated microporous hard carbon)
Detailed Description
The following 1 example of the present invention is given as a further illustration of the invention and is not intended to limit the scope of the invention.
1) 3.0g of phenol is dissolved in 90ml of deionized water, the PH of the solution is regulated to 8, a beaker is placed in a water bath kettle at 60 ℃, 7.75g of formaldehyde solution with the mass fraction of 37% is added for prepolymerization for 30min, the reaction solution is transferred into a hydrothermal reaction kettle for reaction for 12h at 180 ℃, and the product is washed by the deionized water and dried to obtain the phenolic resin.
2) And (3) placing the phenolic resin in a muffle furnace filled with argon, heating to 800 ℃ at a heating rate of 5 ℃/min, and carbonizing for 2 hours to obtain the hard carbon microspheres.
3) Uniformly mixing hard carbon microspheres with KOH in a mass ratio of 1:2, placing the mixture in a muffle furnace filled with argon, heating to 700 ℃ at a heating rate of 5 ℃/min, activating for 1h, cooling, removing excessive KOH by using hydrochloric acid, fully washing to neutrality by using deionized water, and drying to obtain the microporous hard carbon microspheres.
4) 150mg of microporous carbon spheres are placed in a fluorination reaction kettle, vacuumizing is carried out, and when the temperature is raised to 250 ℃, mixed gas (20:80) of fluorine gas and nitrogen gas is introduced for reaction for 4 hours, so that the hard carbon fluoride with a microporous structure is obtained.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (4)
1. A method for preparing high-performance fluorocarbon battery by using microporous hard carbon as precursor comprises scanning image as shown in figure 1 and transmitting image as shown in figure 2.
2. The method for producing microporous hard carbon according to claim 1, characterized by comprising the steps of:
adding formaldehyde solution and phenol into deionized water in sequence to form a homogeneous solution, regulating the pH to 8, prepolymerizing in a water bath kettle at 60 ℃ for 30min, transferring to a hydrothermal reaction kettle, reacting at 180 ℃ for 12h, washing and drying the product, carbonizing in a muffle furnace at 800 ℃ (argon atmosphere) for 2h to obtain phenolic resin-based hard carbon, and then chemically activating to obtain the hard carbon with a micropore structure.
3. The chemical activation method as claimed in claim 2, characterized in that hard carbon and KOH are mixed uniformly in a ratio of 1:2, burned in a muffle furnace at 600-800 ℃ for 1h (argon atmosphere), then excess alkali is removed by means of hydrochloric acid solution, washed with deionized water, dried and then fluorinated.
4. A process according to claim 3, wherein the microporous hard carbon is placed in a reaction vessel and evacuated to a certain temperatureAt the temperature of 200-300 ℃, a mixed gas (F) of fluorine gas and nitrogen gas is introduced 2 ∶N 2 =20:80), for 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211068969.3A CN117682506A (en) | 2022-09-02 | 2022-09-02 | Method for preparing high-performance fluorocarbon battery by taking microporous hard carbon as precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211068969.3A CN117682506A (en) | 2022-09-02 | 2022-09-02 | Method for preparing high-performance fluorocarbon battery by taking microporous hard carbon as precursor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117682506A true CN117682506A (en) | 2024-03-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211068969.3A Pending CN117682506A (en) | 2022-09-02 | 2022-09-02 | Method for preparing high-performance fluorocarbon battery by taking microporous hard carbon as precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117682506A (en) |
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2022
- 2022-09-02 CN CN202211068969.3A patent/CN117682506A/en active Pending
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