CN113526486A - Ultrahigh-sulfur-content hard carbon material and preparation method and application thereof - Google Patents
Ultrahigh-sulfur-content hard carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021385 hard carbon Inorganic materials 0.000 title abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 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 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- YOLFWWMPGNMXFI-UHFFFAOYSA-N 2-thiophen-2-yldisulfanylthiophene Chemical compound C=1C=CSC=1SSC1=CC=CS1 YOLFWWMPGNMXFI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000002441 reversible effect Effects 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- -1 and accordingly Chemical compound 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the field of new energy, and discloses an ultrahigh sulfur content hard carbon material, and a preparation method and application thereof. The preparation method comprises the steps of taking trithiophene and dithienyl disulfide as initial raw materials, and constructing a reticular polymer precursor with high sulfur content and stable skeleton through simple concentrated sulfuric acid crosslinking reaction; and after carbonization, obtaining the carbon material with ultrahigh sulfur content, wherein the sulfur content can reach more than 30%. When the carbon material is used as a negative electrode material of a sodium ion battery, sulfur atoms in the carbon material can provide a large number of sodium storage sites, so that the specific capacity of the carbon electrode is greatly improved. Under the current density of 100mA/g, the reversible sodium storage capacity of the prepared carbon material exceeds 800mAh/g, which is far better than that of the current most of sodium-ion battery cathode materials. The method is simple, easy to operate and environment-friendly, and the prepared carbon material has excellent electrochemical performance and is expected to be applied to industrial large-scale production.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to a hard carbon material with ultrahigh sulfur content, and a preparation method and application thereof.
Background
Batteries have been playing an extremely important role in modern human life and society. In recent years, lithium ion batteries have been widely used in the fields of portable electronic equipment products and electric vehicles by virtue of the advantages of large capacity, high efficiency, long cycle life and the like, and are incorporated into the aspects of people's lives. However, the lithium resource on the earth is very limited, and the world faces the crisis of lithium resource shortage after 65 years by calculating the current lithium consumption rate, so that the search for a substitute of the lithium ion battery is particularly urgent. Sodium, a congenic element of lithium, has similar physicochemical properties to lithium, and accordingly, sodium-ion batteries have comparable performance to lithium-ion batteries. Meanwhile, the sodium element is abundant in nature, and accounts for about 2.83% of the earth crust storage amount, and the price of the sodium element is far lower than that of lithium. Therefore, the development of commercial sodium ion batteries is one of the most reliable solutions to the danger of lithium resources.
The cathode material is used as a key component of the sodium ion battery, and the performance of the cathode material directly determines the performance of the sodium ion battery. At present, graphite is the first choice of negative electrode material for commercial lithium ion batteries, but the sodium storage capacity of the graphite is low (35 mAh/g), and the graphite hardly has scale application prospect. The amorphous carbon has rich defects and microporous structure, and can realize Na+Is one of the most promising negative electrode materials of sodium ion batteries. However, the reversible sodium storage capacity of amorphous carbon materials is usually below 350mAh/g, and it is difficult to meet the development demand of high-energy sodium ion batteries. Sulfur doping of carbon-based materials is an important means for achieving high capacity and high reversibility of energy storage. However, the current sulfur doping method often requires an additional sulfur source, the process is complex, and it is difficult to prepare carbon materials with ultra-high sulfur content, so the performance improvement of the electrode material is still limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a hard carbon material with ultrahigh sulfur content; the method takes trithiophene or dithienyl disulfide as a raw material, and prepares the trithiophene or dithienyl disulfide by a concentrated sulfuric acid crosslinking method, and the preparation process is simple and easy to implement, green and environment-friendly.
The invention also aims to provide the ultra-high sulfur content hard carbon material prepared by the preparation method, and the material has excellent sodium storage performance.
The invention further aims to provide application of the ultra-high sulfur content hard carbon material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an ultra-high sulfur content carbon material comprises the following operation steps:
(1) uniformly mixing and stirring a monomer and a cross-linking agent, carrying out cross-linking reaction on the obtained mixture to obtain a black blocky solid, and grinding the black blocky solid into black powder;
(2) and (3) placing the black powder in a tube furnace, heating to 500-1200 ℃ at a heating rate of 0.5-5 ℃/min in an inert gas atmosphere, and carbonizing for 0.5-5 h to obtain the carbon material with the ultrahigh sulfur content.
The monomer in the step (1) is more than one of trithiophene and dithienyl disulfide; the cross-linking agent is more than one of sulfuric acid and chlorosulfonic acid; the molar ratio of the monomer to the cross-linking agent is 1: 0.5-1: 3; the temperature of the crosslinking reaction is 80-200 ℃, and the time of the crosslinking reaction is 1-24 hours.
The carbon skeleton of the carbon material is an amorphous carbon skeleton, and the sulfur element is uniformly distributed in the amorphous carbon skeleton, wherein the mass percentage of the sulfur element is more than 30%. The content of the sulfur element can be regulated and controlled by the carbonization temperature between 500 ℃ and 900 ℃.
The carbon material with ultrahigh sulfur content is applied to the negative electrode material of the sodium ion battery, and the reversible sodium storage capacity of the negative electrode material of the sodium ion battery reaches more than 800mAh/g under the current density of 100 mA/g; the reversible sodium storage capacity is maintained above 500mAh/g at a current density of 1A/g.
The negative electrode material of the sodium-ion battery is prepared by the following method: dropping and mixing the carbon material with the ultrahigh sulfur content, the conductive carbon black and the polyvinylidene fluoride binder in a mass ratio of 50-80: 10-30: 10-20 to prepare slurry, and coating the slurry on a copper foil to obtain the sodium-ion battery negative electrode material.
Compared with the prior art, the invention has the following advantages and effects:
(1) tests show that the sulfur content of the carbon material can reach more than 30 percent, which is far higher than that of the most sulfur-doped carbon material at present; when the carbon material is used as a negative electrode material of a sodium ion battery, the reversible capacity of the carbon material with the ultrahigh sulfur content can reach more than 800mAh/g under the current density of 0.1A/g. When the current density is 1A/g, the capacity is still kept above 500mAh/g, and the capacity is not obviously attenuated after the circulation for 300 circles at the current density. The electrochemical properties show that the carbon material with ultrahigh sulfur content has extremely high sodium storage capacity, is superior to most of the carbon negative electrodes of sodium ion batteries at present, and has great application potential. (ii) a
(2) The preparation method is simple, easy to operate and environment-friendly, and the carbon material prepared by the method has excellent electrochemical performance and is expected to be applied to the industry to realize large-scale production.
Drawings
FIG. 1 is an XRD pattern of an ultra-high sulfur content carbon material prepared from a polythiophene feedstock of the present invention.
FIG. 2 shows the mapping of the scanning electron microscope for the ultra-high sulfur content carbon material prepared from the raw material of trithiophene.
FIG. 3 is a graph of the constant current charge and discharge electrochemical properties of an ultra high sulfur carbon material, wherein (a) is the constant current charge and discharge electrochemical properties of an ultra high sulfur carbon material synthesized from a trithiophene starting material, and (b) is the constant current charge and discharge electrochemical properties of an ultra high sulfur carbon material synthesized from a dithiophene starting material; as can be seen from the figure, the capacity gradually decreases and the cycle performance becomes more stable as the carbonization temperature increases.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Respectively weighing corresponding trithiophene monomers and dithienyl disulfide monomers according to the molar ratio of concentrated sulfuric acid to trithiophene of 3:1 and the molar ratio of concentrated sulfuric acid to dithienyl disulfide of 2:1, and measuring the corresponding concentrated sulfuric acid. Firstly, fully stirring a concentrated sulfuric acid crosslinking agent and a monomer in a beaker to fully dissolve the concentrated sulfuric acid crosslinking agent and the monomer, then putting the beaker into a vacuum drying oven to react for 12 hours at 120 ℃, and carrying out free radical crosslinking polymerization reaction under the action of the crosslinking agent. Black blocky products are obtained after the reaction. And then heating at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing at 500 ℃, 700 ℃ and 900 ℃ respectively to finally obtain the carbon material with the ultrahigh sulfur content. As shown by XRD in fig. 1, the diffraction peak of carbon becomes more and more pronounced with increasing temperature. The obtained carbon material with the ultrahigh sulfur content, conductive carbon black and polyvinylidene fluoride (PVDF) are mixed and ground uniformly according to the mass ratio of 70:20:10, N-methyl pyrrolidone (NMP) with proper amount is added to be prepared into slurry, the slurry is uniformly mixed and coated on a copper foil, and after the slurry is dried in vacuum at 50 ℃ for 12 hours, the slurry is rolled to obtain the negative electrode material of the sodium-ion battery.
Punching the prepared negative electrode material of the sodium-ion battery into
Of wafers of
The metal sodium sheet is a counter electrode, the Celgard2500 polypropylene microporous membrane is used as a diaphragm, and 1mol/LLIPF6The electrolyte solution of/DMC + EMC + EC (volume ratio of 1:1:1) is filled in a glove box filled with argon to form a button cell. A battery testing system (CT2001A) is adopted to test the battery, and the charging and discharging voltage range is 0-3V. As can be seen from Table 3, at 100mAg-1The initial discharge capacity of the battery of the carbon material with ultra-high sulfur content prepared by the trithiophene monomer can reach 757.5mAhg at 500 ℃, 700 ℃ and 900 ℃ respectively-1、789.5mAhg-1、311.3mAhg-1The capacitance and the primary charge capacity of the capacitor can respectively reach 612.5mAhg-1、667.3mAhg-1、283.4mAhg-1The capacitance of (c). The initial coulombic efficiencies were 80.86%, 84.52%, 91.04%, respectively. As can be seen from Table 3, the carbon material with ultra-high sulfur content prepared from dithienyl disulfide monomer is 100mAg-1At a current density of 500 ℃ and 700 DEG CThe initial discharge capacity of the battery can reach 1268.8mAhg at 900 DEG C-1、721.6mAhg-1、347.6mAhg-1The primary charging capacity of the capacitor can reach 1188.4mAhg respectively-1、630.6mAhg-1、315.2mAhg-1The capacitance of (c). The initial coulombic efficiencies were 93.67%, 87.39%, and 90.68%, respectively. The material has higher capacity performance.
Example 2
This example examines the effect on sulfur content at different carbonization temperatures, as shown in table 1. The conditions were the same as in example 1 except that the carbonization temperature was different from that in example 1. Also as shown by fig. 2, the sulfur is well distributed homogeneously in the carbon material.
Table 1 influence of different carbonization temperatures on the sulfur content.
| Crosslinking carbonization temperature of trithiophene | Post-carbonization sulfur content (%) |
| 500℃ | 36.6 |
| 700℃ | 32.86 |
| 900℃ | 14.21 |
Example 3
This example examines the effect of different carbonization temperatures on the electrochemical properties of the material, 1000mAg-1The constant current charge and discharge results are shown in Table 2. The carbonization temperature was different from that of example 1, and other conditions were the same asExample 1 was identical. Fig. 3 (a) and (b) are graphs of the cycle performance of trithiophene and dithienyl disulfide, respectively.
TABLE 2 Effect of different carbonization temperatures on electrochemical Performance of carbon materials with ultra-high Sulfur content
Example 4
This example examines the influence of different carbonization temperatures on the electrochemical properties of the material, 100mAg-1The constant current charge and discharge results are shown in Table 3. The conditions were the same as in example 1 except that the carbonization temperature was different from that in example 1.
TABLE 3 influence of different carbonization temperatures on electrochemical Performance of carbon materials with ultra-high Sulfur content
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A preparation method of an ultra-high sulfur content carbon material is characterized by comprising the following operation steps:
(1) uniformly mixing and stirring a monomer and a cross-linking agent, carrying out cross-linking reaction on the obtained mixture to obtain a black blocky solid, and grinding the black blocky solid into black powder;
(2) and (3) placing the black powder in a tube furnace, heating to 500-1200 ℃ at a heating rate of 0.5-5 ℃/min in an inert gas atmosphere, and carbonizing for 0.5-5 h to obtain the carbon material with the ultrahigh sulfur content.
2. The method of claim 1, wherein: the monomer in the step (1) is more than one of trithiophene and dithienyl disulfide; the cross-linking agent is more than one of sulfuric acid and chlorosulfonic acid; the molar ratio of the monomer to the cross-linking agent is 1: 0.5-1: 3; the temperature of the crosslinking reaction is 80-200 ℃, and the time of the crosslinking reaction is 1-24 hours.
3. An ultra-high sulfur content carbon material produced by the production method according to claim 1, characterized in that: the carbon skeleton of the carbon material is an amorphous carbon skeleton, and the sulfur element is uniformly distributed in the amorphous carbon skeleton, wherein the mass percentage of the sulfur element is more than 30%.
4. The use of the ultra-high sulfur content carbon material of claim 3 in a negative electrode material for sodium ion batteries, wherein: the reversible sodium storage capacity of the negative electrode material of the sodium ion battery reaches more than 800mAh/g under the current density of 100 mA/g; the reversible sodium storage capacity is maintained above 500mAh/g at a current density of 1A/g.
5. Use according to claim 4, characterized in that: the negative electrode material of the sodium-ion battery is prepared by the following method: the method comprises the steps of dropwise adding N-methyl pyrrolidone into an ultrahigh-sulfur-content carbon material, conductive carbon black and a binder polyvinylidene fluoride in a mass ratio of 50-80: 10-30: 10-20, mixing to prepare a slurry, and coating the slurry on a copper foil to obtain the sodium-ion battery negative electrode material.
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| CN115304051A (en) * | 2022-08-29 | 2022-11-08 | 广东工业大学 | Soft carbon material containing closed pores and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931855A (en) * | 2016-06-04 | 2016-09-07 | 常州大学 | Synthesizing method of nitrogen and sulfur co-doped carbon/polyaniline composite material and application to supercapacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105931855A (en) * | 2016-06-04 | 2016-09-07 | 常州大学 | Synthesizing method of nitrogen and sulfur co-doped carbon/polyaniline composite material and application to supercapacitor |
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Application publication date: 20211022 |