CN112837947B - Nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from inorganic-cellulose raw material, and preparation and application thereof - Google Patents
Nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from inorganic-cellulose raw material, and preparation and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920002678 cellulose Polymers 0.000 title claims abstract description 62
- 239000001913 cellulose Substances 0.000 title claims abstract description 62
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 48
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 19
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 37
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000007833 carbon precursor Substances 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- 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
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Abstract
The invention relates to a nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from an inorganic-cellulose raw material, and preparation and application thereof, wherein the preparation process comprises the following steps: stirring and mixing cellulose and ammonia water under the condition of water bath, carrying out suction filtration, washing and drying the obtained product to obtain ammoniated cellulose; adding ammoniated cellulose and ferric sulfate into water, carrying out hydrothermal reaction, and carrying out pre-carbonization treatment to obtain a pre-carbonized product; and uniformly mixing the pre-carbonized product with an activating agent and water, calcining at high temperature, washing and drying to obtain the nitrogen and sulfur co-doped layered porous carbon hybrid material. Compared with the prior art, the method has the advantages that a large amount of cellulose existing in nature is used as the carbon precursor, the cost is saved, the method belongs to a green process, meanwhile, the metal elements are doped to improve the pseudo-capacitance performance of the porous carbon material, and the electricity storage capacity of the electrode material is greatly enhanced.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of a super capacitor, in particular to a nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from an inorganic-cellulose raw material, and preparation and application thereof.
Background
Energy has a profound influence on human life, at present, fossil fuels still make a contribution to most of energy demands in the world, and with global economic expansion and population explosion, the consumption of fossil fuels such as coal, petroleum and natural gas is increased sharply. In recent years, new energy sources such as solar energy, tidal energy, hydraulic energy, wind energy, biological energy and the like are mentioned, researched and applied continuously. Supercapacitors, as a new type of energy storage device, have found a number of applications in consumer electronics, medical devices and hybrid vehicles due to their high power density and good cycling stability.
Supercapacitors have attracted considerable attention because they can provide high power density, excellent cycling stability, and the potential to evolve to approach the energy density of conventional batteries. Compared with electrode materials such as some conductive polymers and metal oxides, the specific capacity of the porous carbon material is lower. Although carbon-based electrode materials have many advantages as electric double layer electroactive materials, their smaller potential window and specific capacitance have not been able to fully meet the demands of technological development. To solve this problem, it is generally compounded with a metal oxide or the like to improve the overall electrochemical performance thereof. In order to further improve the electrochemical properties of the porous carbon material, numerous researchers often introduce heteroatoms into the porous carbon material, and numerous research results indicate that the method works effectively. In the periodic table, nitrogen atoms are adjacent to carbon atoms, and theoretically, nitrogen and sulfur atoms are relatively easy to replace carbon atoms by physical or chemical methods. Therefore, the hot research focus of people in the research field focuses on the direction of heteroatom-doped porous carbon materials.
The biomass activated carbon has the advantages of high specific surface area, low cost, long cycle life, high conductivity, environmental friendliness, simple method and the like. Therefore, a suitable method for preparing the N, S-codoped layered porous carbon hybrid material by using biomass as a raw material is needed to be searched, so that the N, S-codoped layered porous carbon hybrid material can be used for industrial production of electrode materials of supercapacitors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from an inorganic-cellulose raw material, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to protect a method for preparing a nitrogen-sulfur co-doped layered porous carbon hybrid material from an inorganic-cellulose raw material, which is characterized by comprising the following steps of:
s1: stirring and mixing cellulose and ammonia water under the condition of water bath, carrying out suction filtration, washing and drying the obtained product to obtain ammoniated cellulose;
s2: adding the ammoniated cellulose obtained in the step S1 and ferric sulfate into water, moving the ammoniated cellulose and ferric sulfate into a reactor to perform hydrothermal reaction, and performing pre-carbonization treatment on the obtained reaction product to obtain a pre-carbonized product;
s3: and (3) uniformly mixing the pre-carbonized product obtained in the step (S2) with an activating agent and water, drying, calcining at a high temperature, washing and drying the calcined product to obtain the nitrogen-sulfur co-doped layered porous carbon hybrid material.
Further, the mass fraction of the ammonia water in the S1 is 25%, and the mass ratio of the cellulose to the ammonia water is 10-15.
Further, the temperature of the water bath condition in the S1 is 60-80 ℃, and the water bath time is 8-12h.
Further, the mass ratio of the ammoniated cellulose to ferric sulfate in the S2 is (8-12): 1.
further, the temperature of the hydrothermal reaction in S2 is 180 ℃, and the hydrothermal reaction time is 24h.
Further, the step of the pre-carbonization in S2 is drying the product after the hydrothermal reaction and heating the product in an inert gas, wherein the temperature of the pre-carbonization is 500 ℃ and the time is 2 hours.
Further, the mass ratio of the pre-carbonized product to the activating agent in S3 is 1 (1 to 2), and the activating agent is KOH.
Further, the high-temperature calcination in S3 is carried out in an inert gas atmosphere, the calcination temperature is 600-900 ℃, the time is 2-5 h, and the temperature rise rate during calcination is 5-10 ℃/min.
The second purpose of the invention is to protect the nitrogen and sulfur co-doped layered porous carbon hybrid material obtained by the preparation method.
The third purpose of the invention is to protect the nitrogen and sulfur co-doped electrode material of the super capacitor, which comprises a hybrid carbon material, carbon black and PTFE, wherein the mass ratio of the hybrid carbon material to the carbon black is 8 (0.8-1.2) to (0.8-1.2), and the hybrid carbon material is the nitrogen and sulfur co-doped layered porous carbon hybrid material.
Compared with the prior art, the invention has the following technical advantages:
1) The method utilizes the cellulose extracted from natural biomass as the carbon precursor, saves cost, is cheap and environment-friendly, and belongs to a green process. The cellulose structure contains a large amount of carboxyl and hydroxyl, and the added ammonia water can react with the carboxyl and the hydroxyl to destroy the original structure of the cellulose, so that the cellulose can form a layered structure better, and nitrogen elements are successfully doped in the reaction. The purpose of adding iron sulfate is to introduce elemental sulfur. The carbon precursor is doped with N and S double elements, so that the electrochemical performance of the material is greatly improved, and the sulfur element can be fully doped in the excess ammoniated cellulose. The carbonization of some tissue structures of part of cellulose can affect the rear high-temperature calcination effect due to high pre-carbonization temperature, the pre-carbonization effect is not obvious when the pre-carbonization temperature is less than 500 ℃, and the pre-carbonization product can be fully activated due to slight excess of the activating agent KOH. Because potassium ions and the pre-carbonized product generate surface organic potassium salt, the surface organic potassium salt has influence on the surface electron cloud of aromatic carbon, thereby increasing the activity of the material. The inert gas is used as the protective gas to avoid oxidation and other impurities are doped. The cellulose inherently contains N element, the N element returns to the crystal lattice again through certain reaction conditions, and the self-doping is realized, while the doped ferro-sulphur element is foreign, and the self-doping has the advantage that other impurities do not need to be introduced while the target element is not introduced.
2) The porous carbon material prepared by the method has a multi-stage porous structure, and the electricity storage capacity of the electrode material is greatly enhanced.
3) In the invention, ferric sulfate plays a role in doping N and S elements into the carbon material to provide more chemical active sites, so that the carbon material generates pseudo capacitance, the electrochemical stability of the carbon material is improved, the specific capacitance is improved, and the carbon material has an important influence on the appearance of a solid product.
Drawings
Fig. 1 is a TEM image of the nitrogen-sulfur co-doped layered porous carbon hybrid material obtained in the technical scheme.
FIG. 2 shows that the current density of the N, S-codoped layered porous carbon hybrid material prepared in example 1 in the technical scheme is 0.5Ag -1 GCD curve of time.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
In the following examples, the cellulose raw material was purchased from ordinary cellulose of Shanghai Tatan company.
Unless otherwise indicated, all materials or processing techniques are conventional and commercially available in the art.
Example 1:
(1) Mixing cellulose with 25% 4 Stirring and mixing OH in water bath, wherein the temperature of the water bath is 60 ℃, and the stirring time is 12h;
(2) Putting the ammoniated cellulose obtained by suction filtration and washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) adding 3g of the dried ammoniated cellulose and 0.3g of ferric sulfate in the step (2) into 30ml of deionized water, performing ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃, and the hydrothermal time is 24h.
(4) Filtering, washing and drying the hydrothermal product deionized water and ethanol in the step (3), and then carrying out high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:1, calcining at a high temperature of 600 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at a drying temperature of 60 ℃ for 12 hours, and drying to obtain a nitrogen and sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.
As shown in fig. 2, it can be observed from the TEM image that the nitrogen-sulfur co-doped carbon material has a more uniform lattice, and it can be presumed that more iron is doped, which indicates that hydrothermal method plays a good role in metal doping.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and the GCD curve were tested using 6MKOH solution as the electrolyte. The GCD peaks around 210 as shown in fig. 2, indicating that the electrochemical performance of this material is good.
Example 2:
(1) Mixing cellulose with 25% NH 4 Stirring and mixing OH in water bath, wherein the temperature of the water bath is 70 ℃, and the stirring time is 10 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration and washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) adding 3g of the dried ammoniated cellulose and 0.3g of ferric sulfate in the step (2) into 30ml of deionized water, performing ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃, and the hydrothermal time is 24h.
(4) Filtering, washing and drying the hydrothermal product deionized water and ethanol in the step (3), and then carrying out high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:1, calcining at a high temperature of 700 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at a drying temperature of 80 ℃ for 10 hours, and drying to obtain a nitrogen and sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.8.
And (3) testing the electrochemical performance of the nitrogen and sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and GCD curve were tested using 6MKOH solution as the electrolyte. 0.5Ag of nitrogen and sulfur co-doped carbon material for super capacitor prepared in example 2 -1 The GCD graph of (A) shows that the peak value is about 210, which shows that the electrochemical performance of the material is good.
Example 3:
(1) Mixing cellulose with 25% NH 4 Stirring and mixing OH in water bath, wherein the water bath temperature is 80 ℃, and the stirring time is 12 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) adding 3g of the dried ammoniated cellulose and 0.3g of ferric sulfate in the step (2) into 30ml of deionized water, performing ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃, and the hydrothermal time is 24h.
(4) Filtering and washing the hydrothermal products deionized water and ethanol in the step (3), drying, and performing high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:2, calcining at the high temperature of 700 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at the drying temperature of 90 ℃ for 12 hours, and drying to obtain the nitrogen-sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and the GCD curve were tested using 6MKOH solution as the electrolyte. Example 3 preparation of nitrogen and sulfur co-doped carbon material for supercapacitor at 0.5Ag -1 The GCD of (1) shows that the peak value appears at about 200, which shows that the electrochemical performance of the material is good.
Example 4:
(1) Mixing cellulose with 25% NH 4 OH is stirred and mixed in water bath, the temperature of the water bath is 110 ℃, and the stirring time is 8 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration and washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) taking 3g of the ammoniated cellulose and 0.3g of ferric sulfate dried in the step (2), adding the ammoniated cellulose and the ferric sulfate into 30ml of deionized water, and carrying out ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24h.
(4) Filtering and washing the hydrothermal products deionized water and ethanol in the step (3), drying, and performing high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:1, calcining at a high temperature of 900 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at a drying temperature of 110 ℃ for 10 hours, and drying to obtain a nitrogen and sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.2.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and GCD curve were tested using 6MKOH solution as the electrolyte. Nitrogen and sulfur co-doped carbon material prepared in example 4 for super capacitor at 0.5Ag -1 The GCD of (1) shows that the peak value appears at about 220, which shows that the electrochemical performance of the material is good.
Example 5:
(1) Mixing cellulose with 15% 4 OH is stirred and mixed in water bath, the temperature of the water bath is 90 ℃, and the stirring time is 12 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration and washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) taking 3g of the ammoniated cellulose and 0.3g of ferric sulfate dried in the step (2), adding the ammoniated cellulose and the ferric sulfate into 30ml of deionized water, and carrying out ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24h.
(4) Filtering and washing the hydrothermal products deionized water and ethanol in the step (3), drying, and performing high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:1, calcining at a high temperature of 800 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at a drying temperature of 100 ℃ for 10 hours, and drying to obtain a nitrogen and sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.
And (3) testing the electrochemical performance of the nitrogen and sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and the GCD curve were tested using 6MKOH solution as the electrolyte. Example 5 preparation of nitrogen and sulfur co-doped carbon material for supercapacitor at 0.5Ag -1 The GCD of (1) shows that the peak value appears at about 200, which shows that the electrochemical performance of the material is good.
Example 6:
(1) Mixing cellulose with 25% 4 OH is stirred and mixed in water bath, the temperature of the water bath is 110 ℃, and the stirring time is 9 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration and washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) adding 3g of the dried ammoniated cellulose and 0.3g of ferric sulfate in the step (2) into 30ml of deionized water, performing ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃, and the hydrothermal time is 24h.
(4) Filtering and washing the hydrothermal products deionized water and ethanol in the step (3), drying, and performing high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:2, the high-temperature calcination is carried out at the temperature of 900 ℃ for 2 hours, the obtained calcined sample is washed and dried, the sample is washed to be neutral by dilute hydrochloric acid and deionized water, the sample is placed in a vacuum drying oven, the drying temperature is 110 ℃, the drying time is 9 hours, and the nitrogen and sulfur co-doped porous carbon material is obtained through drying;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.8.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and GCD curve were tested using 6MKOH solution as the electrolyte. Example 6 preparation of nitrogen and sulfur co-doped carbon material for supercapacitor at 0.5Ag -1 The GCD of (1) shows that the peak value appears at about 220, which shows that the electrochemical performance of the material is good.
Example 7
(1) Mixing cellulose with 25% NH 4 OH is stirred and mixed in water bath, the temperature of the water bath is 110 ℃, and the stirring time is 9 hours;
(2) Putting the ammoniated cellulose obtained by suction filtration washing in a vacuum drying oven, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
(3) And (3) taking 3g of the ammoniated cellulose and 0.3g of ferric sulfate dried in the step (2), adding the ammoniated cellulose and the ferric sulfate into 30ml of deionized water, and carrying out ultrasonic hydrothermal treatment for 0.5h, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24h.
(4) Filtering and washing the hydrothermal products deionized water and ethanol in the step (3), drying, and performing high-temperature pre-carbonization by using a tubular furnace, wherein the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
(5) Uniformly mixing the pre-carbonized product in the step (4) with KOH and deionized water, and then calcining at high temperature, wherein the mass ratio of the pre-carbonized product to the activating agent is 1:1, calcining at a high temperature of 600 ℃ for 2 hours, washing and drying the calcined sample, washing the sample to be neutral by using dilute hydrochloric acid and deionized water, placing the sample in a vacuum drying oven, drying at a drying temperature of 80 ℃ for 12 hours, and drying to obtain a nitrogen and sulfur co-doped porous carbon material;
(6) And (3) grinding the carbon material obtained in the step (5), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8.2.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
by electrochemical engineeringAnd (4) standing, and carrying out electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and the GCD curve were tested using 6MKOH solution as the electrolyte. Example 7 preparation of nitrogen and sulfur co-doped carbon material for supercapacitor at 0.5Ag -1 The GCD of (1) shows that the peak value appears at about 200, which shows that the electrochemical performance of the material is good.
In the preparation process of the nitrogen-phosphorus co-doped carbon material for the supercapacitor, the process conditions can be adjusted randomly within the following process ranges according to requirements, and the excellent electrode performance can be realized: wherein in the step (1), the water bath temperature is 60 to 80 ℃, and the water bath time is 8 to 12h; in step (2), cellulose is reacted with 25% NH 4 The mass ratio of OH is 10% -15%; in the step (3), the mass ratio of the ammoniated cellulose to the ferric sulfate is (8-12): 1; in the step (3) and the step (4), the drying temperature is 60 to 110 ℃, and the time is 6 to 12h; in the step (4), the temperature of the pre-carbonization is 500 ℃, and the time is 2h; in the step (4), the mass ratio of the calcined sample to the KOH is 1 (1 to 2); in the step (5), the process conditions for continuing the high-temperature calcination are as follows: the calcination temperature is 600 to 900 ℃, the calcination time is 2 to 5h, the high-temperature calcination is carried out under the nitrogen atmosphere, and the heating rate is 5 to 10 ℃/min; grinding the obtained nitrogen-phosphorus co-doped carbon material, mixing the ground carbon material with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain a nitrogen-sulfur co-doped electrode material for a supercapacitor; the mass ratio of the nitrogen-sulfur co-doped carbon material to the carbon black to the PTFE is 8 (0.8 to 1.2) to (0.8 to 1.2).
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The method for preparing the nitrogen-sulfur co-doped layered porous carbon hybrid material from the inorganic-cellulose raw material is characterized by comprising the following steps of:
s1: stirring and mixing cellulose and ammonia water under the water bath condition, carrying out suction filtration, washing and drying the obtained product to obtain the ammoniated cellulose;
s2: adding the ammoniated cellulose and ferric sulfate obtained in the step S1 into water, moving the ammoniated cellulose and ferric sulfate into a reactor for hydrothermal reaction, and carrying out pre-carbonization treatment on the obtained reaction product to obtain a pre-carbonized product;
s3: uniformly mixing the pre-carbonized product obtained in the step S2 with an activating agent and water, drying, calcining at high temperature, washing and drying the calcined product to obtain the nitrogen and sulfur co-doped layered porous carbon hybrid material;
the mass ratio of the ammoniated cellulose to ferric sulfate in the S2 is (8-12): 1;
the step of the pre-carbonization in the S2 is to dry a product after the hydrothermal reaction and put the product into inert gas for heating, wherein the temperature of the pre-carbonization is 500 ℃ and the time is 2 hours;
the mass ratio of the pre-carbonized product to the activating agent in the S3 is 1 (1 to 2), and the activating agent is KOH.
2. The method for preparing the nitrogen-sulfur co-doped layered porous carbon hybrid material from the inorganic-cellulose raw material according to claim 1, wherein the mass fraction of the ammonia water in S1 is 25%, and the mass ratio of the cellulose to the ammonia water is 10-15.
3. The method for preparing the nitrogen-sulfur co-doped layered porous carbon hybrid material from the inorganic-cellulose raw material according to claim 1, wherein the temperature of the water bath in S1 is 60-80 ℃ and the water bath time is 8-12h.
4. The method for preparing the nitrogen-sulfur co-doped layered porous carbon hybrid material from the inorganic-cellulose raw material according to claim 1, wherein the hydrothermal reaction in S2 is carried out at 180 ℃ for 24 hours.
5. The method for preparing the nitrogen-sulfur co-doped layered porous carbon hybrid material from the inorganic-cellulose raw material according to claim 1, wherein high-temperature calcination in S3 is carried out in an inert gas atmosphere, the calcination temperature is 600 to 900 ℃, the calcination time is 2 to 5h, and the temperature rise rate during calcination is 5 to 10 ℃/min.
6. A nitrogen and sulfur co-doped layered porous carbon hybrid material prepared by the method of any one of claims 1 to 5.
7. A nitrogen and sulfur co-doped electrode material for a supercapacitor is characterized by comprising a hybrid carbon material, carbon black and PTFE in a mass ratio of 8 (0.8-1.2) to (0.8-1.2), wherein the hybrid carbon material is the nitrogen and sulfur co-doped layered porous carbon hybrid material in claim 6.
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