CN116040601A - Hard carbon material with high Fisher particle size core ring structure and application thereof - Google Patents
Hard carbon material with high Fisher particle size core ring structure and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 38
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005121 nitriding Methods 0.000 claims abstract description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 235000001759 Citrus maxima Nutrition 0.000 claims description 2
- 244000276331 Citrus maxima Species 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 240000000716 Durio zibethinus Species 0.000 claims description 2
- 235000006025 Durio zibethinus Nutrition 0.000 claims description 2
- 241000283070 Equus zebra Species 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 241000219071 Malvaceae Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 230000002633 protecting effect Effects 0.000 abstract 2
- 230000003139 buffering effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000008093 supporting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of hard carbon cathode materials, and relates to a hard carbon material with a high Fisher-Tropsch particle size core ring structure and application thereof. The preparation method comprises the following steps: (1) crushing biomass raw materials to obtain precursor raw materials; (2) Mixing a precursor raw material and an organic solution containing a catalyst to obtain pretreatment powder; (3) Carrying out heat treatment on the pretreated powder raw material to obtain a core homogeneous layer, and carrying out high-temperature treatment to obtain a transition layer on the surface of the core homogeneous layer; (4) rapidly nitriding the raw material wrapping the transition layer; (5) Sintering the rapidly nitrided raw material at a high temperature in an inert atmosphere; and (6) introducing carbon source gas, and continuing carbonization at a high temperature. The obtained material is of a core ring structure, the outer part is a surface layer of a multi-hollow reticular hard sphere layer, the supporting and protecting effects are realized, the middle part is a transition layer, the buffering and protecting effects are realized, the fixing effect is realized on an inner core homogeneous region, the innermost layer is of a homogeneous lamellar hard carbon structure, and a large number of holes are reserved for sodium storage.
Description
Technical Field
The invention belongs to the technical field of hard carbon cathode materials, and relates to a hard carbon material with a high Fisher-Tropsch particle size core ring structure and application thereof.
Background
In recent years, due to the highly developed photovoltaic power generation and the large popularization of the water power generation, the energy storage demand is rapidly increased, and electrochemical energy storage is a relatively effective energy storage mode currently acknowledged. The lithium battery is the most focused new energy at present, and has been widely applied and researched, and the invention and the preparation of lithium cobaltate and ternary lithium batteries change the production and living rhythms of people. However, the increasing price and the great demand for energy storage make the lithium battery have low adaptation in the field of energy storage, so that the sodium ion battery similar to the working principle of the lithium ion battery is receiving a great deal of attention.
The extremely abundant sodium element reserves bring extremely low cost, and the comprehensive cost performance is higher, and the sodium ion battery has wide prospect. Sodium ion batteries have not been of interest for many years because of their somewhat lower energy density than lithium ion batteries. Meanwhile, in terms of materials, the research and development of some positive electrode materials basically meet the application requirements, but the negative electrode materials still restrict the practical application of the sodium ion battery.
At present, among sodium battery anode materials, a hard carbon material is considered as the most promising sodium battery anode material, and can firstly show electrochemical performance close to that of a graphite anode of a lithium battery, and the performance is stable; and secondly, the high-temperature treatment energy consumption and the temperature are low, the raw materials are rich and easy to obtain, and the sodium intercalation amount is high. However, hard carbon has a low specific capacity and has lower first-round charge-discharge efficiency than graphite. How to improve the electrochemical performance of hard carbon materials is a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the prior art and provide a hard carbon material with a high Fisher-Tropsch particle size core ring structure and application thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the hard carbon material with the high Fisher-Tropsch particle size core ring structure comprises the following steps:
(1) Crushing biomass raw materials by using a ball mill to obtain precursor raw materials;
(2) Mixing the precursor raw material with an organic solution containing a catalyst, soaking and uniformly granulating to obtain pretreatment powder;
(3) Placing the pretreated powder raw material into a muffle furnace for heat treatment to obtain a core homogeneous layer, and then performing high-temperature treatment on the homogeneous layer to obtain a transition layer on the surface of the homogeneous layer;
(4) Rapidly nitriding the raw material wrapping the transition layer by using low-pressure gas;
(5) Putting the rapidly nitrided raw material into a high-temperature carbonization furnace, heating at a constant heating rate, and sintering the raw material at a high temperature in an inert atmosphere;
(6) Introducing carbon source gas into the high-temperature carbonization furnace, and continuously carbonizing at high temperature;
(7) And cooling to room temperature to obtain the hard carbon material with the high Fisher-Tropsch particle size core ring structure.
The invention realizes the generation of the core ring by depositing the catalyst in the raw material and adopting a vapor deposition method. The outer part of the core ring structure is a surface layer of a multi-hollow netlike hard ball layer, the middle part of the core ring structure is a transition layer, the core ring structure has a buffer protection function, the inner core homogenizing region is fixed, and the innermost layer is a homogenizing flaky hard carbon structure and is provided with a large number of holes for storing sodium.
In the step (1), the biological raw material is any one or the combination of at least two selected from basswood, rice hulls, straw, shaddock peel, durian peel, zebra and oak; the rotating speed of the ball mill is 100-500r/min, and the ball milling time is 2-10h.
The precursor raw material in the step (1) is firstly screened and refined to obtain a biomass precursor fine powder raw material with the particle size within the range of 100-800 meshes, and then the biomass precursor fine powder raw material is used in the step (2).
In the step (2), the catalyst is any one or a combination of at least two of ferric chloride, nickel chloride, cobalt chloride, magnesium chloride and molybdenum chloride;
the organic solvent adopted by the organic solution containing the catalyst is any one or a combination of at least two of N-methyl pyrrolidone, carbon tetrachloride, cyclohexane and tetrahydrofuran;
the mass fraction of the catalyst in the catalyst-containing organic solution is 0.5-5wt%;
in the step (2), the soaking time is 1-8 hours; the mass ratio of the catalyst-containing organic solution to the precursor raw material is (1-5): 100.
If the soaking time of the precursor fine powder raw material by the salt solution is too short, the catalyst is difficult to enter the material, which is unfavorable for the growth of the subsequent carbon nano tube, but the soaking time is too long, and the preparation process time is longer.
In the step (3), the heat treatment temperature is 200-400 ℃ and the heat treatment time is 2-8h; the temperature of the further high-temperature treatment is 700-900 ℃, the treatment time is 20-40min, and the heating rate is 3-5 ℃/min.
In the step (5), the high-temperature sintering temperature is 1000-1200 ℃ and the high-temperature sintering time is 2-10h.
In the step (6), the carbon source gas comprises any one or a combination of at least two of methane, ethylene and acetylene; the carbonization temperature is 600-1000 ℃, and the carbonization time is 1-6 hours.
A hard carbon anode material comprising a hard carbon material employing a high fischer-tropsch particle size core ring structure as described above.
The negative electrode of the sodium ion battery is prepared from the hard carbon negative electrode material.
The energy density and the first coulombic efficiency of the sodium ion battery can be improved by preparing the negative electrode of the sodium ion battery from the hard carbon material with the high Fisher-Tropsch particle size core ring structure.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a schematic diagram of a hard carbon material with a high Fisher-Tropsch particle size core ring structure.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
100g of straw is washed and dried, and then crushed by using a ball mill at 300r/min to obtain coarse powder. And screening the coarse powder to obtain the biomass precursor finely-divided raw material of between 100 and 200 meshes. Mixing the precursor finely-divided raw materials with a tetrahydrofuran solution with the mass fraction of nickel chloride of 1 wt%, and soaking for 1h to obtain the further pretreated granulated fine powder raw materials. Placing the pretreated fine powder raw material into a muffle furnace at 300 o C, performing heat treatment for 2 hours. Heating the heat-treated raw material at 800 ℃ for 30min, and then carrying out rapid low-pressure nitriding on the raw material. Putting the low-pressure nitrided raw material into a high-temperature carbonization furnace to obtain a mixture of 3 o The temperature rising rate of C/min is raised to 1000 o And C, sintering the raw materials at high temperature in an inert atmosphere for 3 hours. Introducing methane carbon source gas, and heating to 800 deg.f o And C, firing for 1 hour, and cooling to room temperature to obtain the carbon material with irregular blocky morphology, namely the Gao Feishi granularity core ring structure hard carbon material.
The hard carbon negative electrode material is assembled into a button cell, and the mass ratio of the raw materials of the button cell, namely the hard carbon negative electrode material, CMC (sodium carboxymethylcellulose) and ketjen black is 8:1:1. and (5) detecting the electrochemical performance of the button cell.
Example 2
The precursor infiltration solvent of the example 1 is changed into N-methyl pyrrolidone to prepare the hard carbon material, and the rest preparation methods and parameters are consistent.
Example 3
The catalyst content of example 2 was reduced to 0.5wt% to prepare a hard carbon material, and the remaining preparation methods were consistent with the parameters.
Example 4
The catalyst of the example 1 is changed into a mixed material of ferric chloride and cobalt chloride with the mass ratio of 1:1 to prepare a hard carbon material, and the rest preparation methods and parameters are kept consistent.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. The preparation method of the hard carbon material with the high Fisher-Tropsch particle size core ring structure is characterized by comprising the following steps:
(1) Crushing biomass raw materials by using a ball mill to obtain precursor raw materials;
(2) Mixing the precursor raw material with an organic solution containing a catalyst, soaking and uniformly granulating to obtain pretreatment powder;
(3) Placing the pretreated powder raw material into a muffle furnace for heat treatment to obtain a core homogeneous layer, and then performing high-temperature treatment on the homogeneous layer to obtain a transition layer on the surface of the homogeneous layer;
(4) Rapidly nitriding the raw material wrapping the transition layer by using low-pressure gas;
(5) Putting the rapidly nitrided raw material into a high-temperature carbonization furnace, heating at a constant heating rate, and sintering the raw material at a high temperature in an inert atmosphere;
(6) Introducing carbon source gas into the high-temperature carbonization furnace, and continuously carbonizing at high temperature;
(7) And cooling to room temperature to obtain the hard carbon material with the high Fisher-Tropsch particle size core ring structure.
2. The high fischer-tropsch particle size core ring structure hard carbon material according to claim 1 wherein: in the step (1), the biological raw material is any one or the combination of at least two selected from basswood, rice hulls, straw, shaddock peel, durian peel, zebra and oak; the rotating speed of the ball mill is 100-500r/min, and the ball milling time is 2-10h.
3. The high fischer-tropsch particle size core ring structure hard carbon material according to claim 1 wherein: the precursor raw material in the step (1) is firstly screened and refined to obtain a biomass precursor fine powder raw material with the particle size within the range of 100-800 meshes, and then the biomass precursor fine powder raw material is used in the step (2).
4. A high fischer-tropsch particle size core ring structure hard carbon material according to claim 3 wherein: in the step (2), the catalyst is any one or a combination of at least two of ferric chloride, nickel chloride, cobalt chloride, magnesium chloride and molybdenum chloride;
the organic solvent adopted by the organic solution containing the catalyst is any one or a combination of at least two of N-methyl pyrrolidone, carbon tetrachloride, cyclohexane and tetrahydrofuran;
the mass fraction of the catalyst in the catalyst-containing organic solution is 0.5-5wt%.
5. The hard carbon material with the high fischer-tropsch particle size core ring structure according to claim 4, wherein: in the step (2), the soaking time is 1-8 hours; the mass ratio of the catalyst-containing organic solution to the precursor raw material is (1-5): 100.
6. The high fischer-tropsch particle size core ring structure hard carbon material according to claim 1 wherein: in the step (3), the heat treatment temperature is 200-400 ℃ and the heat treatment time is 2-8h; the temperature of the further high-temperature treatment is 700-900 ℃, the treatment time is 20-40min, and the heating rate is 3-5 ℃/min.
7. The high fischer-tropsch particle size core ring structure hard carbon material according to claim 1 wherein: in the step (5), the high-temperature sintering temperature is 1000-1200 ℃ and the high-temperature sintering time is 2-10h.
8. The high fischer-tropsch particle size core ring structure hard carbon material according to claim 1 wherein: in the step (6), the carbon source gas comprises any one or a combination of at least two of methane, ethylene and acetylene; the carbonization temperature is 600-1000 ℃, and the carbonization time is 1-6 hours.
9. A hard carbon anode material, characterized in that the hard carbon anode material comprises a hard carbon material adopting the high fischer-tropsch particle size core ring structure according to any one of claims 1 to 8.
10. A sodium ion battery, wherein the negative electrode of the sodium ion battery is prepared from the hard carbon negative electrode material according to claim 9.
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| CN114380284A (en) * | 2022-01-12 | 2022-04-22 | 河北坤天新能源科技有限公司 | Hard carbon negative electrode material and preparation method and application thereof |
| CN114804073A (en) * | 2022-03-29 | 2022-07-29 | 中国科学院广州能源研究所 | Biomass carbon nanotube and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109088046A (en) * | 2018-08-17 | 2018-12-25 | 河南英能新材料科技有限公司 | A kind of preparation method of modification lithium-ion battery electrode |
| US20210322960A1 (en) * | 2018-09-03 | 2021-10-21 | Northwest University | Supported transistion metal carbide catalyst and one-step synthesis method theefore |
| CN111146416A (en) * | 2019-12-19 | 2020-05-12 | 安普瑞斯（南京）有限公司 | Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery |
| CN114380284A (en) * | 2022-01-12 | 2022-04-22 | 河北坤天新能源科技有限公司 | Hard carbon negative electrode material and preparation method and application thereof |
| CN114804073A (en) * | 2022-03-29 | 2022-07-29 | 中国科学院广州能源研究所 | Biomass carbon nanotube and preparation method and application thereof |
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