CN116715216B - Preparation method of hard carbon with high specific surface area and application of hard carbon in sodium ion battery - Google Patents
Preparation method of hard carbon with high specific surface area and application of hard carbon in sodium ion battery Download PDFInfo
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- CN116715216B CN116715216B CN202310462752.9A CN202310462752A CN116715216B CN 116715216 B CN116715216 B CN 116715216B CN 202310462752 A CN202310462752 A CN 202310462752A CN 116715216 B CN116715216 B CN 116715216B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 title claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013067 intermediate product Substances 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 20
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000005554 pickling Methods 0.000 claims abstract description 17
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims abstract description 17
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical compound OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010000 carbonizing Methods 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 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 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 229920000805 Polyaspartic acid Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 108010064470 polyaspartate Proteins 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 graphite compound Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- H01M4/36—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
-
- 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 relates to a preparation method of cheap hard carbon with high specific surface, which comprises the following steps: mixing DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine, ball milling, and preserving the temperature at 300-500 ℃ for 3.0. 3.0 h-6 h to obtain an intermediate product; carbonizing the intermediate product at 1100-1300 ℃ in an inert gas atmosphere, preserving heat for 0.5-5h, and pickling to obtain the hard carbon material. The preparation method disclosed by the invention is simple to operate, wide in raw material sources, simple and easy to obtain, and cost is saved.
Description
Technical Field
The invention relates to a preparation method of cheap hard carbon with high specific surface area and application thereof in sodium ion batteries, belonging to the field of carbon materials.
Background
At present, the lithium resource in China mainly depends on import, so that searching for an alternative or alternative energy storage technology is an under-the-eye technical focus; among the potential substitutes for lithium batteries, sodium ion batteries are favored because of their advantages of abundant reserves, low cost, high safety, and the like. But the performance of the negative electrode material still restricts the further improvement of the performance of the sodium ion battery. Among the current common sodium ion battery anode materials, carbon-based materials are the first choice for studying sodium storage anode materials because of the advantages of wide sources, abundant resources, various structures, long service life and the like. The graphite material is difficult to form a sodium intercalation graphite compound as a negative electrode material of a sodium ion battery, and only a small amount of Na+ can be stored in the graphite, so that the reversible capacity is inhibited; the soft carbon material is easy to cause the change of the interlayer spacing when sodium ions undergo an intercalation and deintercalation reaction, and graphitizable soft carbon is easy to graphitize at high temperature, the interlayer spacing can be reduced, and the sodium storage capacity of the material is reduced; the hard carbon material has large interlayer spacing, more defects and vacancies and higher sodium storage capacity, but has relatively high cost, so that the large-scale application of the hard carbon material is restricted.
Therefore, how to simply and economically prepare hard carbon which can be used for the negative electrode of the sodium ion battery becomes a research hot spot of people at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of cheap hard carbon with high specific surface area and application of the hard carbon to a sodium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
subject 1
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine, ball milling, and preserving the temperature at 300-500 ℃ for 3.0. 3.0 h-6 h to obtain an intermediate product;
B. carbonizing the intermediate product at 1100-1300 ℃ in an inert gas atmosphere, preserving heat for 0.5-5h, and pickling to obtain the hard carbon material.
As a preferred embodiment of the invention, the mass ratio of DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine is 5-15:2.5-7.5:2.5-7.5:1.5-4.5:2.5-7.5.
As a preferred embodiment of the present invention, the mass ratio of DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine is 10:5:5:3:5.
as a preferred embodiment of the present invention, the ball milling rotation speed is 100-600 rpm; the ball milling time is 5-12h.
As a preferred embodiment of the invention, said step A is incubated at 300℃for 5h.
As a preferred embodiment of the invention, the intermediate product in the step B is carbonized at 1200 ℃ under the inert gas atmosphere, and the temperature is kept for 1.5h.
As a preferred embodiment of the invention, the acid washing step is to acid wash the intermediate product in 5 wt% hydrochloric acid solution.
As a preferred embodiment of the present invention, the specific steps of carbonization are: heating to 1100-1300 ℃ at a heating rate of 5-10 ℃/min.
Subject matter II
The invention also provides application of the hard carbon material prepared by the preparation method of the low-cost high-specific surface hard carbon, which is used for the negative electrode material of the sodium ion battery.
Subject III
The invention also provides a sodium ion battery, which comprises a hard carbon material prepared by adopting the preparation method of the low-cost high-specific surface hard carbon of the technical subject one.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
1. the preparation method provided by the invention adopts the precise collocation of DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine, so that the operation is simple, the raw material sources are wide, the method is simple and easy to obtain, and the cost is saved; and the prepared hard carbon material has a very high practical application prospect in the field of sodium batteries.
2. The DL-aspartic acid selected in the invention is a cheap biomass, and has low price and rich resources; compared with polyaspartic acid, chitosan and chitin, the hard carbon prepared by the method is low in cost and better in battery performance when used for sodium batteries; the melamine selected by the invention is doped with nitrogen in situ, and is polymerized with aspartic acid to form a high polymer, so that the carbon fixation content is improved, the material defect is increased, and the capacity is provided for sodium storage.
Drawings
Fig. 1 is an SEM image of the hard carbon material prepared in example 1 of the present invention.
FIG. 2 is a graph showing the specific surface absorption of the hard carbon material prepared in example 1 of the present invention.
FIG. 3 is a Raman diagram of a hard carbon material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Each of the materials in the formulations of the present invention are commercially available. Polyvinylpyrrolidone used in the following examples and comparative examples: average molecular weight is 58000, chitosan: average molecular weight 10000, polyaspartic acid: molecular weight is 5000, chitin: molecular weight 2000.
Example 1
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g potassium formate, 5g polyvinylpyrrolidone, 3g ammonium chloride and 5g melamine, ball milling for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
1-3, respectively carrying out SEM (scanning electron microscope), specific surface adsorption and Raman spectrum analysis characterization on the prepared hard carbon material; therefore, the invention successfully prepares the hard carbon material, and the specific surface area of the hard carbon material is as high as 3426 m 2 /g。
Example 2
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 5 gDL-aspartic acid, 7.5g potassium formate, 2.5g polyvinylpyrrolidone, 4.5g ammonium chloride and 2.5g melamine, ball milling for 12 hours at a ball milling speed of 100 revolutions per minute, and then preserving heat at 500 ℃ for 3 hours to obtain an intermediate product;
B. heating to 1100 ℃ at a heating rate of 5 ℃/min, carbonizing the intermediate product at 1100 ℃ in a nitrogen gas atmosphere, preserving heat for 5 hours, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Example 3
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 15 gDL-aspartic acid, 2.5g potassium formate, 7.5g polyvinylpyrrolidone, 1.5g ammonium chloride and 7.5g melamine, ball milling for 5 hours at a ball milling speed of 600 revolutions per minute, and then preserving heat at 400 ℃ for 6 hours to obtain an intermediate product;
B. heating to 1300 ℃ at a heating rate of 10 ℃/min, carbonizing the intermediate product at 1300 ℃ in a nitrogen gas atmosphere, preserving heat for 0.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Example 4
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 12 gDL-aspartic acid, 6g potassium formate, 6g polyvinylpyrrolidone, 3.6g ammonium chloride and 4g melamine, ball milling for 6 hours at a ball milling speed of 200 revolutions per minute, and then preserving heat at 400 ℃ for 4 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 8 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 2h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 1
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g polyvinylpyrrolidone, 3g ammonium chloride and 5g melamine, ball-milling for 8 hours at a ball-milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 2
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g potassium formate, 5g polyvinylpyrrolidone and 5g melamine, ball-milling for 8 hours at a ball-milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 3
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g polyvinylpyrrolidone and 5g melamine, ball-milling for 8 hours at a ball-milling speed of 300 rpm, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 4
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing and ball milling 10g of chitosan, 5g of potassium formate, 5g of polyvinylpyrrolidone, 3g of ammonium chloride and 5g of melamine for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 5
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10g of polyaspartic acid, 5g of potassium formate, 5g of polyvinylpyrrolidone, 3g of ammonium chloride and 5g of melamine, ball milling for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 6
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10g of chitin, 5g of potassium formate, 5g of polyvinylpyrrolidone, 3g of ammonium chloride and 5g of melamine, ball milling for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 7
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g potassium formate, 5g polyvinylpyrrolidone, 1g ammonium chloride and 5g melamine, ball milling for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Comparative example 8
The preparation method of the cheap hard carbon with the high specific surface comprises the following steps:
A. mixing 10 gDL-aspartic acid, 5g potassium formate, 5g polyvinylpyrrolidone, 5g ammonium chloride and 5g melamine, ball milling for 8 hours at a ball milling speed of 300 revolutions per minute, and then preserving heat at 300 ℃ for 5 hours to obtain an intermediate product;
B. heating to 1200 ℃ at a heating rate of 6 ℃/min, carbonizing the intermediate product at 1200 ℃ in a nitrogen gas atmosphere, preserving heat for 1.5h, and then pickling in 5 wt% hydrochloric acid solution for 3 times to obtain the hard carbon material.
Application example 1
Taking a sodium sheet as an anode, mixing the prepared hard carbon material with acetylene black and polyvinylidene fluoride according to a mass ratio of 8:1:1, mixing and grinding, and then dropwise adding N-methyl pyrrolidone while grinding to prepare slurry. And uniformly coating the slurry on a copper box, and heating and drying to obtain the working electrode.
The preparation method of the electrolyte comprises the following steps: the configuration volume ratio is 3:1 propylene carbonate and diethyl carbonate; sodium perchlorate is dissolved in a mixed solution to prepare a solution of one mole per liter containing fluoroethylene carbonate as an additive in a ratio of five percent by volume to form a relatively compact solid electrolyte membrane.
Putting a glass microfiber diaphragm, a sodium metal sheet serving as a reference electrode, a working electrode, a CR2032 battery shell and a gasket into a glove box filled with argon gas to assemble a half battery, and testing the half battery by adopting a LAND CT2001A battery testing instrument manufactured by the GmbH, wherein the specific capacity of the battery is tested under the following conditions: performing charge and discharge test under the current density of C/10 by using constant current charge and discharge conditions; the specific capacity test conditions after 1000 cycles are: the test was performed under the condition that the discharge cut-off voltage was 0.01V and the charge cut-off voltage was 3V. The battery performance test results are shown in table 1 below:
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The preparation method of the hard carbon with the high specific surface area is characterized by comprising the following steps:
A. mixing DL-aspartic acid, potassium formate, polyvinylpyrrolidone, ammonium chloride and melamine, ball milling, and preserving the temperature at 300-500 ℃ for 3.0. 3.0 h-6 h to obtain an intermediate product;
B. carbonizing the intermediate product at 1100-1300 ℃ in an inert gas atmosphere, preserving heat for 0.5-5h, and pickling to obtain a hard carbon material;
the mass ratio of DL-aspartic acid to potassium formate to polyvinylpyrrolidone to ammonium chloride to melamine is 10:5:5:3:5.
2. the method for producing hard carbon with high specific surface area according to claim 1, wherein the ball milling rotation speed is 100-600 rpm; the ball milling time is 5-12h.
3. The method for producing hard carbon with high specific surface area according to claim 1, wherein the step a is performed at 300 ℃ for 5 hours.
4. The method for preparing hard carbon with high specific surface area according to claim 1, wherein the intermediate product in the step B is carbonized at 1200 ℃ under inert gas atmosphere, and is kept for 1.5 hours.
5. The method for producing hard carbon with high specific surface area according to claim 1, wherein the pickling step is pickling in 5 wt% hydrochloric acid solution.
6. The method for preparing hard carbon with high specific surface area according to claim 1, wherein the specific steps of carbonization are as follows: heating to 1100-1300 ℃ at a heating rate of 5-10 ℃/min.
7. Use of a hard carbon material prepared by the method for preparing a hard carbon with a high specific surface area according to any one of claims 1 to 6, for a negative electrode material of a sodium ion battery.
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