CN110759326A - Doped porous carbon material, preparation method thereof and porous carbon-based electrode material - Google Patents
Doped porous carbon material, preparation method thereof and porous carbon-based electrode material Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 239000007772 electrode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000003929 acidic solution Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- WBZFUFAFFUEMEI-UHFFFAOYSA-M Acesulfame k Chemical group [K+].CC1=CC(=O)[N-]S(=O)(=O)O1 WBZFUFAFFUEMEI-UHFFFAOYSA-M 0.000 claims description 6
- 229960004998 acesulfame potassium Drugs 0.000 claims description 6
- 235000010358 acesulfame potassium Nutrition 0.000 claims description 6
- 239000000619 acesulfame-K Substances 0.000 claims description 6
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229940085605 saccharin sodium Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 15
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
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- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000005539 carbonized material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
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- 239000006181 electrochemical material Substances 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- -1 sulfate Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01G11/24—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, 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
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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
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- H—ELECTRICITY
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- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a doped porous carbon material, which comprises the following steps: calcining organic salt containing heteroatoms and alkali metal ions serving as porous carbon material precursors under the protection of inert gas, wherein the heteroatoms are non-metal atoms of a third main group, a fifth main group and a sixth main group; and treating the calcined product with an acidic solution to obtain the heteroatom-doped porous carbon material. The invention also relates to a doped porous carbon material and a porous carbon-based electrode material.
Description
Technical Field
The invention relates to the technical field of functional porous carbon materials, in particular to a doped porous carbon material, a preparation method thereof and a porous carbon-based electrode material.
Background
The demand for high energy density and high power density memory devices has been greatly promoted by the development of portable electronic products and electric vehicles in modern society. Supercapacitors have attracted considerable attention because of their high power density and superior cycling stability. In general, electrode materials play a crucial role in supercapacitors, energy storage occurs primarily through charge accumulation at the electrode/electrolyte interface, and thus the performance of a supercapacitor is closely related to the structure and composition of the electrode material.
The carbon material has the advantages of wide source, low preparation cost, large specific surface area, strong chemical stability and the like, and is widely applied to the super capacitor. Compared with other carbon materials (graphene and carbon nanotubes), the porous carbon material has the advantages of good conductivity, high specific surface area, porous structure, mild reaction conditions and the like, and particularly the porous carbon material containing the heteroatoms can further improve the electrochemical performance of the carbon material, so that the heteroatom-doped porous carbon material is rapidly developed into a novel electrochemical material.
In order to realize the doping of the heteroatom into the carbon skeleton, additional heteroatom additives such as a nitrogen source, a sulfur source and the like, such as thiourea, ammonium persulfate, melamine and the like, need to be added into an original carbon source reagent, and the production cost is increased. In addition, the template method not only requires an expensive template, but also consumes a lot of time for complicated subsequent processing. Chemical activation requires the use of corrosive or toxic activators KOH, NaOH, ZnCl2And the like, have higher requirements on production equipment and cause certain harm to the environment.
Therefore, how to prepare the doped porous carbon material in a manner of simple operation process and low cost is a problem which needs to be solved urgently.
Disclosure of Invention
Based on this, there is a need to provide a method for preparing doped porous carbon material from a single precursor.
Correspondingly, the invention also provides a doped porous carbon material and a porous carbon-based electrode material.
The invention provides a preparation method of a doped porous carbon material, which comprises the following steps:
calcining organic salt containing heteroatoms and alkali metal ions serving as porous carbon material precursors under the protection of inert gas, wherein the heteroatoms are non-metal atoms of a third main group, a fifth main group and a sixth main group; and
and treating the calcined product with an acidic solution to obtain the heteroatom-doped porous carbon material.
In one embodiment, the alkali metal ion is Na+Or K+。
In one embodiment, the organic salt has a molecular weight of 100 to 500.
In one embodiment, the heteroatom is one or more of a sulfur atom, a nitrogen atom, a phosphorus atom, and a boron atom.
In one embodiment, the heteroatoms are sulfur atoms and nitrogen atoms.
In one embodiment, the organic salt is acesulfame potassium or saccharin sodium.
In one embodiment, the calcining temperature is 600-800 ℃, and the calcining time is 0.5-1 hour.
In one embodiment, H in the acidic solution+The concentration of (B) is 3 to 7 mol/L.
The invention also provides a doped porous carbon material which is prepared by the preparation method of the doped porous carbon material.
In one embodiment, the specific surface area of the doped porous carbon material is 430m2G to 1010m2/g。
In one embodiment, the doped porous carbon material comprises macropores, mesopores and micropores, the pore diameter of the macropores is 0.5-1.5 μm, the pore diameter of the mesopores is 3.5-3.6 nm, and the pore diameter distribution of the micropores is 1.7-1.8 nm.
In one embodiment, the heteroatoms are sulfur atoms and nitrogen atoms, the content of sulfur element in the doped porous carbon material is 3 wt% to 10 wt%, and the content of nitrogen element is 2 wt% to 10 wt%.
The invention further provides a porous carbon-based electrode material which comprises a conductive agent, a binder and the doped porous carbon material.
According to the preparation method of the porous carbon material, organic salt containing heteroatoms and alkali metal ions is used as a single precursor, inorganic salt can be generated in a carbonized material structure after calcination, the generated inorganic salt is etched away by an acidic solution to form the porous carbon material, and the heteroatoms are doped into the porous carbon material in the calcination process to form the doped porous carbon material. The method has the advantages of simple process and low cost, and the prepared porous carbon material has large specific surface area and high heteroatom doping amount, and can be used for preparing electrode materials in a super capacitor.
Drawings
FIG. 1 is a schematic view of the preparation method of the doped porous carbon material according to example 1 of the present invention;
FIG. 2 is an electron microscope scanning photograph of the S-N doped porous carbon material prepared in example 1 of the present invention;
FIG. 3 is an XRD spectrum of carbon element of the S-N doped porous carbon material prepared in example 1 of the present invention;
FIG. 4 is an X-ray photoelectron spectroscopy analysis of the S-N doped porous carbon material prepared in example 1 of the present invention;
FIG. 5 is a graph showing nitrogen adsorption and desorption curves of the S-N doped porous carbon materials prepared in examples 1 to 4 of the present invention;
FIG. 6 is a graph showing pore size distribution of porous carbon material doped with sulfur and nitrogen prepared in examples 1 to 4 of the present invention;
FIG. 7 is an electron microscope scanning photograph of the S-N doped porous carbon material prepared in example 2 of the present invention;
FIG. 8 is an electron microscope scanning photograph of the S-N doped porous carbon material prepared in example 3 of the present invention;
FIG. 9 is an electron micrograph of a S-N doped porous carbon material prepared in example 4 of the present invention;
FIG. 10 is an XRD spectrum of a calcined product in example 1 of the present invention;
FIG. 11 is an XRD spectrum of a calcined product in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, one embodiment of the present invention provides a method for preparing a doped porous carbon material, including the following steps:
s10, calcining organic salt containing heteroatoms and alkali metal ions as a porous carbon material precursor under the protection of inert gas, wherein the heteroatoms are non-metal atoms of a third main group, a fifth main group and a sixth main group; and
and S20, treating the calcined product with an acid solution to obtain the heteroatom-doped porous carbon material.
According to the preparation method of the porous carbon material, alkali metal ions in the organic salt can be used as a catalyst to catalyze carbon atoms in the organic salt to form the carbon material, inorganic salt is generated in the carbon material structure, the generated inorganic salt is etched by an acid solution to form a porous structure, and hetero atoms in the organic salt are doped into the carbon material in the calcining process to form the doped porous carbon material. The method utilizes organic salt containing heteroatoms and alkali metal ions as a single precursor to prepare the doped porous carbon material, and has the advantages of simple process and low cost.
The organic salt in the present invention is a small molecular organic substance, and the molecular weight is preferably 100 to 500. Too high molecular weight results in too low metal ion content and failure to form multilevel pore channels in one step.
In one embodiment, the heteroatom contained in the organic salt is one or more of a sulfur atom, a nitrogen atom, a phosphorus atom, and a boron atom. The heteroatom can change the electronic conductivity in the porous carbon material, adjust the pore structure of the porous carbon material and enlarge the interlayer spacing thereof, thereby obviously improving the specific capacity and the rate performance of the porous carbon material. Preferably, the hetero atoms are a sulfur atom and a nitrogen atom.
In one embodiment, the organic salt is carbonized at high temperature to self-generate inorganic salts, such as sulfate, within the structure of the carbonized material. Preferably, the organic salt has a cyclic carbon skeleton. In one embodiment, the organic salt is a heterocyclic compound containing nitrogen and sulfur. In one example, the organic salt is acesulfame potassium or sodium saccharin.
In one embodiment, the alkali metal ion is Na+Or K+The inorganic salt formed is potassium sulfate or sodium sulfate, which is easier to be treated with acidic solution.
In one embodiment, the temperature of calcination is 600 ℃ to 800 ℃ and the calcination time is 0.5 hours to 1 hour. The higher the temperature, the greater the porosity of the doped porous carbon material and the greater the specific surface area.
In one embodiment, the inert gas is at least one of nitrogen, helium, xenon, argon, preferably argon.
In step S20, the acidic solution may be at least one of hydrochloric acid, sulfuric acid and nitric acid, and H in the acidic solution+The concentration of (B) is 3 to 7 mol/L. The acid solution can etch inorganic salt generated in the carbonized material structure after the organic salt is carbonized at high temperature.
The step of treating the calcined product with an acidic solution may comprise:
and S21, placing the calcined product into an acid solution and stirring.
Preferably, the agitation is carried out at 25 ℃ to 50 ℃, more preferably at 50 ℃, which increases the speed of processing the calcined product. The stirring time is preferably 3 to 5 hours.
Preferably, an organic solvent is added to the acidic solution to increase the miscibility of the carbon material with the acidic solution, preferably anhydrous ethanol.
After the step of treating the calcined product with the acid solution, the method further comprises a step of drying the product treated with the acid solution, wherein the drying temperature is 60-80 ℃, and the drying time can be 12-24 hours.
The step of treating the calcined product with an acidic solution further comprises washing the calcined product treated with an acidic solution after the step of treating the calcined product with an acidic solution before the step of drying. Preferably, washing is repeated using distilled water to remove residual alkali metal ions.
The embodiment of the invention also provides a doped porous carbon material prepared by any one of the preparation methods of the doped porous carbon material. The specific surface area of the doped porous carbon material is 430m2G to 1010m2/g。
The doped porous carbon material comprises macropores, mesopores and micropores, wherein the pore diameter of the macropores is larger than 50nm, the pore diameter of the mesopores is between 2nm and 50nm, and the pore diameter of the micropores is smaller than 2 nm. Due to the existence of alkali metal ions, carbon defects are formed in the heteroatom-doped porous material in the calcining process, so that a microporous structure is formed in the porous carbon material. The multi-level pore structure in the porous carbon material is more beneficial to the electrochemical performance of the material, the micropores can ensure that the material has higher specific surface area and specific capacity, and the macropores provide a channel for rapid electron transmission, so that the rate capability is improved. The pore diameter of the macropore of the doped porous carbon material is 0.5-1.5 mu m, the pore diameter distribution of the mesopore is 3.5-3.6 nm, and the pore diameter distribution of the micropore is 1.7-1.8 nm.
In one embodiment, the porous carbon material doped with organic salts containing heteroatoms and alkali metal ions as the porous carbon material precursor is a porous carbon material doped with sulfur atoms and nitrogen atoms, wherein the content of sulfur elements is 3 wt% to 10 wt%, and the content of nitrogen elements is 2 wt% to 10 wt%.
The invention also provides a porous carbon-based electrode material which comprises a conductive agent, a binder and the doped porous carbon material. The porous carbon-based electrode material can be used as a super-capacitor electrode material.
The following are specific examples
Example 1
(1) 6g of acesulfame potassium powder is weighed and poured into a square boat, the square boat is placed in a high-temperature tube furnace, and inert gas argon is introduced. The calcined product was then removed after stabilization for half an hour at a rate of 3.5 ℃/min up to 300 ℃ and then at a rate of 5 ℃/min up to 800 ℃ for 0.5 h.
(2) And putting the product into a prepared hydrochloric acid solution with the concentration of 5mol/L, adding 20mL of anhydrous ethanol, stirring at the temperature of 50 ℃ for 3h, filtering the solid by using a suction filtration device after stirring, and repeatedly washing the residual K ions in the solid by using distilled water.
(3) And (3) putting the washed solid into an oven, and drying at the temperature of 80 ℃ for 12h to obtain the nitrogen and sulfur co-doped porous carbon material.
The sulfur-nitrogen doped porous carbon material prepared in example 1 is characterized by a Scanning Electron Microscope (SEM), and is found to have a large number of interconnected macroporous structures, wherein the pore diameter is 1-1.5 μm, as shown in FIG. 2.
XRD characterization revealed two broad peaks at about 25.1 ° and 42.5 °, indicating that the sulfur-nitrogen-co-doped porous carbon material prepared in example 1 is an amorphous carbon structure, as shown in fig. 3. In addition, it was also found by XRD characterization that in the XPS element absorption peak of the material, absorption peaks of S and N were observed, indicating that S and N elements were successfully doped into the porous carbon material, as shown in fig. 4. C. H, N, S the concrete contents of each element are respectively: 42.32 wt.%, 1.02 wt.%, 2.70 wt.%, 3.64 wt.%.
The nitrogen adsorption-desorption curve graph obtained by the nitrogen adsorption-desorption isotherm test is shown in fig. 5, and the pore size distribution graph is shown in fig. 6. The specific surface area of the sulfur-nitrogen co-doped porous carbon material prepared in example 1 is calculated to be 1009m2And/g, micropores and mesopores exist in the material, the distribution of the micropores is mainly micropores with the size of about 1.7nm, and the distribution of the mesopores is about 3.5 nm.
Example 2
The procedure was essentially the same as in example 1 except that the temperature was raised to 300 ℃ at a rate of 3.5 ℃/min, stabilized for half an hour, then raised to 700 ℃ at a rate of 5 ℃/min, held for 1 hour, and the product was removed.
The sulfur-nitrogen doped porous carbon material prepared in example 2 was also shown to have a large number of interconnected macroporous structures with pore diameters ranging from 0.5 μm to 1.0 μm, as shown in fig. 7, by characterization of Scanning Electron Microscopy (SEM).
XRD shows that the sulfur and nitrogen co-doped porous carbon material prepared in example 2 is also in an amorphous carbon structure, in XPS element absorption peaks of the material, S and N absorption peaks are also observed, and the specific contents of C, H, N, S elements in the sulfur and nitrogen co-doped porous carbon material prepared in example 2 are as follows: 51.90 wt.%, 2.82 wt.%, 9.19 wt.%, 6.29 wt.%.
The nitrogen adsorption-desorption curve chart obtained by the nitrogen adsorption-desorption isotherm test is shown in FIG. 5The aperture profile is shown in figure 6. The specific surface area of the sulfur-nitrogen co-doped porous carbon material prepared in example 2 was calculated to be 897m2The material mainly comprises micropores with the diameter of about 1.7 nm.
Example 3
The procedure was essentially the same as in example 1 except that the temperature was raised to 300 ℃ at a rate of 3.5 ℃/min, stabilized for half an hour, then raised to 600 ℃ at a rate of 5 ℃/min, held for 1 hour, and the product was removed.
The sulfur-nitrogen doped porous carbon material prepared in example 3 was also shown to have a large number of interconnected macroporous structures, with pore diameters around 0.5 μm, as shown in fig. 8, by characterization of a Scanning Electron Microscope (SEM).
XRD shows that the sulfur and nitrogen co-doped porous carbon material prepared in example 3 is also in an amorphous carbon structure, in XPS element absorption peaks of the material, absorption peaks of S and N are also observed, and the specific contents of C, H, N, S elements in the sulfur and nitrogen co-doped porous carbon material prepared in example 3 are as follows: 53.06 wt.%, 2.58 wt.%, 9.52 wt.%, 9.87 wt.%.
The nitrogen adsorption-desorption curve graph obtained by the nitrogen adsorption-desorption isotherm test is shown in fig. 5, and the pore size distribution graph is shown in fig. 6. The specific surface area of the sulfur-nitrogen co-doped porous carbon material prepared in example 3 is calculated to be 460m2The micropore distribution of the material is about 1.7 nm.
Example 4
The preparation process was substantially the same as in example 1, except that acesulfame potassium was replaced with saccharin sodium.
The sulfur-nitrogen doped porous carbon material prepared in example 4 is characterized by a Scanning Electron Microscope (SEM), and is found to have a large number of interconnected macroporous structures, and the pore diameter is about 0.5 μm to 1.0 μm, as shown in fig. 9.
XRD shows that the sulfur-nitrogen co-doped porous carbon material prepared in example 4 is also in an amorphous carbon structure, in XPS element absorption peaks of the material, absorption peaks of S and N are also observed, and specific contents of C, H, N, S elements in the sulfur-nitrogen co-doped porous carbon material prepared in example 4 are respectively as follows: 55.56 wt.%, 1.933 wt.%, 5.24 wt.%, 23.89 wt.%.
The nitrogen adsorption-desorption curve graph obtained by the nitrogen adsorption-desorption isotherm test is shown in fig. 5, and the pore size distribution graph is shown in fig. 6. The specific surface area of the sulfur-nitrogen co-doped porous carbon material prepared in example 4 was calculated to be 430m2And/g, micropores exist in the material, and the distribution of the micropores is mainly micropores with the diameter of about 1.8 nm.
Verification example 1
The calcined product of example 1 was taken out and directly subjected to XRD characterization without treatment with a hydrochloric acid solution. The data as characterized in fig. 10 is via PDF card: a comparison of 05-0613 shows that the calcined product contains K2SO4It is shown that acesulfame potassium can generate K in the carbon material during the high temperature calcination process2SO4。
Verification example 2
The calcined product of example 4 was taken out and directly subjected to XRD characterization without treatment with a hydrochloric acid solution. The data, as characterized in fig. 11, shows that the calcined product contains other inorganic substances in addition to carbon.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A preparation method of a doped porous carbon material is characterized by comprising the following steps:
calcining organic salt containing heteroatoms and alkali metal ions serving as porous carbon material precursors under the protection of inert gas, wherein the heteroatoms are non-metal atoms of a third main group, a fifth main group and a sixth main group; and
and treating the calcined product with an acidic solution to obtain the heteroatom-doped porous carbon material.
2. The method for producing a doped porous carbon material according to claim 1, wherein the alkali metal ion is Na+Or K+。
3. The method for producing a doped porous carbon material according to claim 1, wherein the molecular weight of the organic salt is 100 to 500.
4. The method for producing a doped porous carbon material according to claim 1, wherein the hetero atom is one or more of a sulfur atom, a nitrogen atom, a phosphorus atom, and a boron atom.
5. The method for producing a doped porous carbon material according to claim 1, wherein the hetero atoms are a sulfur atom and a nitrogen atom.
6. The method for producing a doped porous carbon material according to claim 1, wherein the organic salt is acesulfame potassium or saccharin sodium.
7. The method for producing a doped porous carbon material according to any one of claims 1 to 6, wherein the calcination temperature is 600 ℃ to 800 ℃ and the calcination time is 0.5 hour to 1 hour.
8. A doped porous carbon material, characterized in that it is produced by the method for producing a doped porous carbon material according to any one of claims 1 to 7.
9. The blend of claim 8A hetero-porous carbon material characterized in that the specific surface area of the doped porous carbon material is 430m2G to 1010m2/g。
10. The doped porous carbon material of claim 8, wherein the doped porous carbon material comprises macropores, mesopores and micropores, the macropores have a pore size of 0.5-1.5 μm, the mesopores have a pore size of 3.5-3.6 nm, and the micropores have a pore size distribution of 1.7-1.8 nm.
11. The doped porous carbon material according to claim 8, wherein the hetero atoms are a sulfur atom and a nitrogen atom, and the content of the sulfur element in the doped porous carbon material is 3 to 10 wt% and the content of the nitrogen element is 2 to 10 wt%.
12. A porous carbon-based electrode material, characterized in that the electrode material comprises a conductive agent, a binder and the doped porous carbon material of any one of claims 8 to 11.
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