CN113479885A - Nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material and preparation method thereof - Google Patents
Nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material and preparation method thereof Download PDFInfo
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- 229910021401 carbide-derived carbon Inorganic materials 0.000 title claims abstract description 51
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 238000005530 etching Methods 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 239000012300 argon atmosphere Substances 0.000 claims description 14
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material and a preparation method thereof, and the preparation method comprises the following steps: preparing SiOC powder; preparation of porous siloxic-derived carbon material CDC: preparing a nitrogen and sulfur co-doped silicon-oxygen-carbon derived carbon material: mixing thiourea with a porous silicon-oxygen-carbon derived carbon material CDC (carbon dioxide) by taking thiourea as a precursor of a co-doped N source and S source, and then adding the mixture into deionized water to be uniformly stirred to obtain a mixed solution; placing the mixed solution in a polytetrafluoroethylene reaction kettle, and heating to perform hydrothermal reaction; and after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by using deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom to obtain the nitrogen-sulfur co-doped silicon-oxygen-carbon derived carbon material NSCDC. The NSCDC obtained by the invention has the advantages of high specific surface area, wide pore size distribution range, uniform pore size distribution, three-dimensional network, good etching effect, environmental friendliness and capability of mass production.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material and a preparation method thereof.
Background
The super capacitor has the advantages of ultrahigh power density, overlong service life, rapid charging and discharging capability and the like, and is widely applied to the fields of automobiles, spaceflight, war industry, electronics, medical treatment and the like. The super capacitor may be classified into an electric double layer capacitor, a faraday dummy capacitor, and a hybrid super capacitor according to a charge storage mechanism and a difference in electrode material. Among them, Electric Double Layer Supercapacitors (EDLCs), which exhibit the advantages of better rate capability and longer cycle life despite their low specific capacitance and low energy density, are a type of supercapacitors currently being studied more widely and commercially and which store charge using an electric double layer formed at an electrode/electrolyte interface. Therefore, EDLCs electrode materials should have a large surface area for charge accumulation and should have a suitable pore structure to wet the electrolyte and promote rapid ion movement. Electrode materials for EDLCs are mainly derived from carbon materials with high specific surface area and high electrical conductivity, such as activated carbon, carbon nanotubes, graphene and other nanostructured carbon materials. Carbide-derived carbon (CDC) as a novel porous carbon material has many advantages such as ultra-high specific surface area, adjustable pore size distribution, graded porosity, coexistence of multiple carbon nanostructures (e.g., carbon nanotubes, onion carbon, nanodiamonds, etc.), and the like. However, the preparation of carbide-derived carbon usually uses a toxic gas, chlorine gas, for etching, which not only pollutes the environment, but also threatens the human health, and limits the large-scale application thereof.
Therefore, the preparation of the carbide-derived carbon electrode material with ultrahigh specific surface area, hierarchical nano-porous structure, good chemical wettability and high conductivity by utilizing the green and environment-friendly etching technology and the co-doping means is of great importance for developing high-performance and low-cost EDLCs.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material and a preparation method thereof, and solves the problems of low yield, low specific capacitance, narrow pore size distribution, low energy density and the like of the carbide derived carbon electrode material for the double electric layer super capacitor. The method has the advantages of simple and easily-obtained raw material sources, environment-friendly alkali etching technology and low cost, the prepared NSCDC has ultrahigh specific surface area, a small amount of micropores and a large amount of mesopores exist, the conductivity is good, the volume expansion in the charging and discharging process can be effectively relieved, more ion and electron transmission channels and active sites are provided, the transmission distance is shortened, and better circulation stability is obtained.
The present invention achieves the above-described object by the following technical means.
A preparation method of a nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material comprises the following steps:
preparing SiOC powder;
preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC powder into powder, mixing the SiOC powder with strong alkaline powder, pouring the mixed powder into a mould, and pressing into a massive mixture; heating and etching the massive mixture through a tubular furnace, and cooling to obtain black powder; repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and then drying to obtain the porous silica-carbon derived carbon material CDC;
preparing a nitrogen and sulfur co-doped silicon-oxygen-carbon derived carbon material:
mixing thiourea with a porous silicon-oxygen-carbon derived carbon material CDC (carbon dioxide) by taking thiourea as a precursor of a co-doped N source and S source, and then adding the mixture into deionized water to be uniformly stirred to obtain a mixed solution; placing the mixed solution in a polytetrafluoroethylene reaction kettle, and heating to perform hydrothermal reaction; and after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by using deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom to obtain the nitrogen-sulfur co-doped silicon-oxygen-carbon derived carbon material NSCDC.
Further, the SiOC powder and the strong alkaline powder are mixed according to the mass ratio of 1: 2-4.
Further, the massive mixture is a cylinder, the pressure for pressing the cylindrical block is 20MPa, and the pressure maintaining time is 5 min.
Further, heating and etching the massive mixture in an argon atmosphere at the etching temperature of 700-900 ℃; keeping the temperature in a tubular furnace for 1-3 h after heating, and then cooling to obtain black powder; the etching temperature is too low, the heat preservation time is too short, the etching is incomplete, and the specific surface area is low; the etching temperature is too high, the heat preservation time is too long, and the yield after etching is extremely low.
Further, the washed black powder was dried in a drying oven at 60 ℃ for 24 hours.
Further, mixing the thiourea and the porous silicon-oxygen-carbon derived carbon material CDC according to the mass ratio of 1: 2-6; the temperature of the hydrothermal reaction is 150-180 ℃, and the time of the hydrothermal reaction is 12-18 h; and (3) drying the black precipitate in a drying box at the temperature of 60 ℃ for 24 h.
Further, the preparation of the SiOC powder specifically comprises: grinding the organic silicon resin into fine powder, putting the fine powder into a tube furnace for pyrolysis, heating the fine powder in an argon atmosphere at a heating rate of 5 ℃/min, and taking out the generated SiOC after natural cooling.
Further, the high-temperature cracking temperature of the organic silicon resin is 1000 ℃, and the heat preservation time is 4 hours.
Nitrogen-sulfur-codoped three-dimensional reticular hierarchical porous carbide derived carbon electrode material, which has a microporous and mesoporous hierarchical porous structure, and has a specific surface area of 1900-2900 m2/g。
The invention has the beneficial effects that:
according to the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide derived carbon electrode material and the preparation method thereof, SiOC prepared from organic silicon resin is used as a precursor of carbide derived carbon, the precursor is mixed with strong base and then is pressed and formed, then the porous carbon material with the three-dimensional mesh structure and hierarchical micropores and mesopores is prepared by the high-temperature etching technology, and the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide derived carbon with high doping amount is obtained by a hydrothermal method. The raw material source is simple and easy to obtain in the technology, the alkali etching technology is environment-friendly and low in cost, the prepared NSCDC has an ultrahigh specific surface area, a small number of micropores and a large number of mesopores exist, the conductivity is good, the volume expansion in the charging and discharging process can be effectively relieved, more ion and electron transmission channels and active sites are provided, the transmission distance is shortened, and better circulation stability is obtained. Compared with the prior art, the NSCDC obtained by the method has the advantages of high specific surface area, wide pore size distribution range, uniform pore size distribution, three-dimensional net shape, good etching effect, environmental friendliness and capability of mass production.
Drawings
FIG. 1 is a phase composition diagram of an electrode material in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the electrode material of example 1 of the present invention, wherein FIGS. 2a, 2b and 2c are SEM images at different magnifications.
FIG. 3 is a graph showing the specific capacitance and cycle performance of the electrode material in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "axial," "radial," "vertical," "horizontal," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present invention and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Example 1
Preparing SiOC powder: grinding organic silicon resin into powder, pouring the powder into a crucible, transferring the crucible into a tubular furnace, heating the crucible to 1000 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat for 4 hours, and taking out the SiOC obtained by pyrolysis after cooling to the room temperature;
preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC powder into powder, mixing the grinded SiOC powder with KOH powder according to the mass ratio of 1:4, quickly grinding, and quickly grinding to uniformly mix the SiOC powder and the KOH powder, thereby preventing the etching effect from being influenced by the deliquescence of the strong base powder in the air. In order to ensure that the etching is more uniform and wider micropore and mesopore distribution is obtained, the mixed powder is poured into a mold and then pressed into a 2 x 2cm cylindrical block, the pressure is 20MPa, the pressure maintaining time is 5min, the cylindrical block is placed in a nickel crucible and transferred to a tubular furnace for etching, the temperature is increased to 800 ℃ under the argon atmosphere, the temperature is kept for 1h, and after cooling, the black powder is obtained. The etching temperature is too low, the heat preservation time is too short, the etching is incomplete, and the specific surface area is low; the etching temperature is too high, the heat preservation time is too long, and the yield after etching is extremely low. The proper etching temperature and the heat preservation time can ensure the proper yield of the obtained CDC, so that the proper CDC has high specific surface area and a good hierarchical porous structure. And repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and drying at 60 ℃ for 24 hours to obtain CDC (CDC), wherein the yield after etching reaches 18%.
Preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
taking thiourea as a precursor of a co-doped N source and S source, simultaneously dispersing the thiourea and the prepared CDC powder in 75ml of deionized water according to the mass ratio of 1:4, and stirring for 30min to mix uniformly; and (3) placing the uniformly stirred mixed solution into a 100ml polytetrafluoroethylene reaction kettle, keeping the temperature in an oven at 180 ℃ for 12h, after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom in the oven at 60 ℃ overnight to obtain NSCDC-1. As can be seen from fig. 1 and 2, the prepared nitrogen-sulfur co-doped CDC has an amorphous structure and has a three-dimensional network porous structure. And the specific surface area of the material prepared under this example 1 was 2894.7m2 g-1The NSCDC sample has multimodal distribution within the range of 1.7-3 nm and 3-5 nm, has a micropore and mesopore hierarchical porous structure, can improve more channels for the transfer of electrons and ions, and is beneficial to improving the permeability of the electrolyte; from FIG. 3, it can be seen that at 1A g-1At the current density, the specific capacitance of the obtained composite material is 205F g-1, and the cycle efficiency after 5000 cycles is kept at 92%.
Example 2
Preparing SiOC powder: grinding organic silicon resin into powder, pouring the powder into a crucible, transferring the crucible into a tubular furnace, heating the powder to 1000 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 4h, and taking out the SiOC obtained by pyrolysis after cooling to the room temperature.
Preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC into powder, mixing the grinded SiOC powder with KOH powder according to the mass ratio of 1:4, and quickly grinding to uniformly mix the SiOC powder and the KOH powder, thereby preventing the strong base powder from deliquescing in the air to influence the etching effect. In order to ensure that the etching is more uniform and wider micropore and mesopore distribution is obtained, the mixed powder is poured into a mold and then pressed into a 2 x 2cm cylindrical block, the pressure is 20MPa, the pressure maintaining time is 5min, the cylindrical block is placed in a nickel crucible and transferred into a tubular furnace, the nickel crucible is heated to 800 ℃ in the argon atmosphere and is kept for 1h, and after cooling, the black powder is obtained. And repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and drying at 60 ℃ for 24 hours to obtain CDC (CDC), wherein the yield after etching reaches 12%.
Preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
taking thiourea as a precursor of a co-doped N source and S source, simultaneously dispersing the thiourea and the prepared CDC powder in 75ml of deionized water according to the mass ratio of 1:4, and stirring for 30min to mix uniformly; and (3) placing the uniformly stirred mixed solution into a 100ml polytetrafluoroethylene reaction kettle, keeping the temperature in a 150 ℃ oven for 12h, after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom in a 60 ℃ oven overnight to obtain NSCDC-2. The material prepared under this example 2 had a specific surface area of 2794.2m2 g-1At 1A g-1The specific capacitance of the resulting composite was 200F g at current density-1The cycling efficiency after 5000 cycles remained at 90%.
Example 3
Preparing SiOC powder: grinding organic silicon resin into powder, pouring the powder into a crucible, transferring the crucible into a tubular furnace, heating the powder to 1000 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 4h, and taking out the SiOC obtained by pyrolysis after cooling to the room temperature.
Preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC into powder, mixing the grinded SiOC powder with KOH powder according to the mass ratio of 2:4, and quickly grinding. And pouring the mixed powder into a mold, pressing into a 2 x 2cm cylindrical block, keeping the pressure at 20MPa for 5min, placing the cylindrical block in a nickel crucible, transferring the cylindrical block into a tubular furnace, heating to 900 ℃ in an argon atmosphere, keeping the temperature for 3h, and cooling to obtain black powder. And repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and drying at 60 ℃ for 24 hours to obtain CDC (CDC), wherein the yield after etching reaches 16%.
Preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
taking thiourea as a precursor of a co-doped N source and S source, simultaneously dispersing the thiourea and the prepared CDC powder in 75ml of deionized water according to the mass ratio of 1:2, and stirring for 30min to mix uniformly; and (3) placing the uniformly stirred mixed solution into a 100ml polytetrafluoroethylene reaction kettle, keeping the temperature in an oven at 180 ℃ for 12h, after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom in the oven at 60 ℃ overnight to obtain NSCDC-3. The material prepared under this example 3 had a specific surface area of 2526.3m2 g-1At 1A g-1The specific capacitance of the resulting composite material was 185F g at current density-1The cycling efficiency after 5000 cycles remained at 89%.
Example 4
Preparing SiOC powder: grinding organic silicon resin into powder, pouring the powder into a crucible, transferring the crucible into a tubular furnace, heating the powder to 1000 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 4h, and taking out the SiOC obtained by pyrolysis after cooling to the room temperature.
Preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC into powder, mixing the grinded SiOC powder with KOH powder according to the mass ratio of 2:4, and quickly grinding. And pouring the mixed powder into a mold, pressing into a 2 x 2cm cylindrical block, keeping the pressure at 20MPa for 5min, placing the cylindrical block in a nickel crucible, transferring the cylindrical block into a tubular furnace, heating to 700 ℃ in an argon atmosphere, keeping the temperature for 3h, and cooling to obtain black powder. And repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and drying at 60 ℃ for 24 hours to obtain CDC (controlled release concrete), wherein the yield after etching reaches 19%.
Preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
taking thiourea as a precursor of a co-doped N source and S source, simultaneously dispersing the thiourea and the prepared CDC powder in 75ml of deionized water according to the mass ratio of 1:6, and stirring for 30min to mix uniformly; and (3) placing the uniformly stirred mixed solution into a 100ml polytetrafluoroethylene reaction kettle, preserving the temperature in a 150 ℃ oven for 18h, after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom in a 60 ℃ oven overnight to obtain NSCDC-4. The material prepared under this example 4 had a specific surface area of 1926.1m2 g-1At 1A g-1At a current density, the resulting composite had a specific capacitance of 172F g-1(ii) a The cycling efficiency remained at 88% after 5000 cycles.
Example 5
Preparing SiOC powder: grinding organic silicon resin into powder, pouring the powder into a crucible, transferring the crucible into a tubular furnace, heating the powder to 1000 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 4h, and taking out the SiOC obtained by pyrolysis after cooling to the room temperature.
Preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC into powder, mixing the grinded SiOC powder with KOH powder according to the mass ratio of 1:3, and quickly grinding. And pouring the mixed powder into a mold, pressing into a 2 x 2cm cylindrical block, keeping the pressure at 20MPa for 5min, placing the cylindrical block in a nickel crucible, transferring the cylindrical block into a tubular furnace, heating to 900 ℃ in an argon atmosphere, keeping the temperature for 1h, and cooling to obtain black powder. And repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and drying at 60 ℃ for 24 hours to obtain CDC (CDC), wherein the yield after etching reaches 13%.
Preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
taking thiourea as a precursor of co-doping an N source and an S source, and mixing the thiourea with the S sourceDispersing the prepared CDC powder in 75ml of deionized water according to the mass ratio of 1:4, and stirring for 30min to mix uniformly; and (3) placing the uniformly stirred mixed solution into a 100ml polytetrafluoroethylene reaction kettle, keeping the temperature in an oven at 180 ℃ for 12h, after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom in the oven at 60 ℃ overnight to obtain NSCDC-5. The material prepared under this example 5 had a specific surface area of 2786.2m2 g-1At 1A g-1At a current density, the specific capacitance of the resulting composite material was 189F g-1The cycling efficiency after 5000 cycles remained at 88%.
(comparative example modification or deletion)
It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material is characterized by comprising the following steps of:
preparing SiOC powder;
preparation of porous siloxic-derived carbon material CDC:
grinding the SiOC powder into powder, mixing the SiOC powder with strong alkaline powder, pouring the mixed powder into a mould, and pressing into a massive mixture; heating and etching the massive mixture through a tubular furnace, and cooling to obtain black powder; repeatedly cleaning the black powder by centrifugal water washing until the filtrate is neutral, and then drying to obtain the porous silica-carbon derived carbon material CDC;
preparing nitrogen and sulfur co-doped silicon oxygen carbon derived carbon material NSCDC:
mixing thiourea with a porous silicon-oxygen-carbon derived carbon material CDC (carbon dioxide) by taking thiourea as a precursor of a co-doped N source and S source, and then adding the mixture into deionized water to be uniformly stirred to obtain a mixed solution; placing the mixed solution in a polytetrafluoroethylene reaction kettle, and heating to perform hydrothermal reaction; and after the reaction kettle is naturally cooled to room temperature, repeatedly washing the reaction kettle by using deionized water and alcohol to remove residual thiourea, and drying the black precipitate at the bottom to obtain the nitrogen-sulfur co-doped silicon-oxygen-carbon derived carbon material NSCDC.
2. The preparation method of the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide derived carbon electrode material according to claim 1, wherein the SiOC powder and the strong basic powder are mixed in a mass ratio of 1: 2-4.
3. The preparation method of the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide derived carbon electrode material according to claim 1, wherein the bulk mixture is a cylinder, the pressure for pressing the cylindrical bulk is 20MPa, and the pressure holding time is 5 min.
4. The preparation method of the nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material according to claim 1, wherein the massive mixture is heated and etched in an argon atmosphere at the etching temperature of 700-900 ℃; and (3) keeping the temperature in a tubular furnace for 1-3 h after heating, and then cooling to obtain black powder.
5. The preparation method of the nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material as claimed in claim 1, wherein the black powder after being cleaned is placed in a drying oven with the temperature of 60 ℃ for drying for 24 h.
6. The preparation method of the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide-derived carbon electrode material according to claim 1, wherein the thiourea and the porous silica-carbon-derived carbon material CDC are mixed in a mass ratio of 1: 2-6; the temperature of the hydrothermal reaction is 150-180 ℃, and the time of the hydrothermal reaction is 12-18 h; and (3) drying the black precipitate in a drying box at the temperature of 60 ℃ for 24 h.
7. The method for preparing the nitrogen-sulfur co-doped three-dimensional network hierarchical porous carbide derived carbon electrode material according to claim 1, wherein the preparation of the SiOC powder specifically comprises the following steps: grinding the organic silicon resin into fine powder, putting the fine powder into a tube furnace for pyrolysis, heating the fine powder in an argon atmosphere at a heating rate of 5 ℃/min, and taking out the generated SiOC after natural cooling.
8. The preparation method of the nitrogen-sulfur co-doped three-dimensional hierarchical porous carbide-derived carbon electrode material according to claim 7, wherein the pyrolysis temperature of the organic silicon resin is 1000 ℃, and the holding time is 4 h.
9. The nitrogen-sulfur-codoped three-dimensional network hierarchical porous carbide-derived carbon electrode material prepared by the method according to any one of claims 1 to 8, characterized in that the nitrogen-sulfur-codoped three-dimensional network hierarchical porous carbide-derived carbon electrode material has a microporous and mesoporous hierarchical porous structure, and the specific surface area of the electrode material is 1900-2900 m2/g。
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