CN113948316A - Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon - Google Patents
Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon Download PDFInfo
- Publication number
- CN113948316A CN113948316A CN202110517622.1A CN202110517622A CN113948316A CN 113948316 A CN113948316 A CN 113948316A CN 202110517622 A CN202110517622 A CN 202110517622A CN 113948316 A CN113948316 A CN 113948316A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- sulfur
- nitrogen
- dimensional
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 32
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229940068041 phytic acid Drugs 0.000 claims abstract description 16
- 239000000467 phytic acid Substances 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 15
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 14
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003990 capacitor Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012688 phosphorus precursor Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000012190 activator Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- LFQRKUIOSYPVFY-UHFFFAOYSA-L dipotassium diacetate Chemical compound [K+].[K+].CC([O-])=O.CC([O-])=O LFQRKUIOSYPVFY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon, wherein the preparation method comprises the following steps: s1: preparation of nitrogen source and phosphorus source precursors: firstly, reacting melamine with phytic acid according to a certain molar ratio, and obtaining a nitrogen source and a phosphorus source precursor after the reaction is finished; s2: pretreatment of reactants: grinding phenanthrene, melamine, phytic acid polymer, potassium sulfate and potassium oxalate activator according to a certain mass ratio, and uniformly mixing; s3: preparing three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets: and (5) transferring the reactant obtained in the step (S2) to a tubular furnace for reaction, and removing impurities to obtain the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by the two-dimensional carbon nanosheets. The invention provides a universal path for preparing the heteroatom-doped carbon anode material for the zinc ion hybrid capacitor with high area ratio capacitance.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon.
Background
For zinc ion hybrid capacitors, the performance is largely determined by the performance of the positive electrode material. The preparation method of the common carbon material is a template coupling strong base activation method, the method is easy to cause corrosion of equipment, strong acid is required to be used for neutralization in the post-treatment process, the cost is high, and the environment is polluted.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon, the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets for a zinc ion hybrid capacitor is prepared by a simple and environment-friendly process, and a universal path is provided for preparation of a heteroatom-doped carbon anode material for a high-area-ratio-capacitance zinc ion hybrid capacitor.
The invention provides a preparation method of three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon, which comprises the following steps:
s1: preparation of Nitrogen and phosphorus precursors
Firstly, dissolving melamine in deionized water under the conditions of heating and stirring, then adding phytic acid, and after reaction, freezing, filtering and drying to obtain a nitrogen source and a phosphorus source precursor;
s2: pretreatment of reactants
Grinding phenanthrene, potassium sulfate, potassium oxalate and a nitrogen source and phosphorus source precursor in S1 and uniformly mixing;
s3: preparation of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon
And (5) transferring the reactant obtained in the step (S2) to a tubular furnace, reacting by taking argon as protective gas, and after the reaction is finished, cooling to room temperature and removing impurities to obtain the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by the two-dimensional carbon nanosheets.
Preferably, the heating temperature in the S1 is 60-80 ℃, and the reaction time is 6-12 h.
Preferably, the molar ratio of the melamine to the phytic acid in the S1 is 1: 1-3.
Preferably, the mass ratio of phenanthrene, potassium sulfate, potassium oxalate, nitrogen source and phosphorus source precursor in S2 is 1:0.5-2:2-4: 0.1-0.3.
Preferably, the reaction conditions in S3 are: the flow rate of argon is 3-12mL/min, the temperature is 800-.
The three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon prepared by the method provided by the invention.
The invention provides application of the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon in a zinc ion hybrid capacitor.
Mechanism of action
The three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by the two-dimensional carbon nanosheets is synthesized in the confined space of potassium sulfate through the shearing action of potassium diacetate, wherein the potassium sulfate not only plays a role of a template, but also serves as a sulfur source to be doped with sulfur atoms. In addition, the melamine and phytic acid polymer not only can be used as a nitrogen source and a phosphorus source to introduce N, P heteroatoms under the high-temperature condition, but also can be used for physically activating gas generated under the decomposition condition. The specific mechanism is as follows: firstly, phenanthrene molecules, potassium sulfate, potassium oxalate, melamine and phytic acid polymer are uniformly mixed in a solid state, the phenanthrene molecules are melted and coated on the surfaces of the potassium sulfate, potassium oxalate and melamine-phytic acid polymer in a heating process, and then the surfaces of the phenanthrene molecules are polymerized and carbonized. Along with the rise of the temperature, the potassium oxalate is decomposed to generate carbon dioxide gas, simultaneously, the carbon dioxide reacts with carbon to generate carbon monoxide, and the generated gas activates and forms pores on the surface of the carbon substrate to generate micropores for ion adsorption and mesopores for ion transmission of the electrolyte. In addition, a K simple substance generated by decomposition is embedded into a phenanthrene molecular layer after polymerization and carbonization, and a two-dimensional carbon nanosheet is synthesized under the synergistic shearing action of gas generated by reaction. And then, the carbon nano-sheets are connected with each other to form a three-dimensional honeycomb structure, and the honeycomb structure not only can be used as an electrolyte tank to store electrolyte ions, but also can be used as a channel for ion transmission. In addition, the melamine-phytic acid polymer decomposes to generate gas containing N and P, and then reacts with the carbon substrate to replace C element therein, and N, P heteroatom is introduced; meanwhile, potassium sulfate reacts with the carbon substrate to replace C atoms in the carbon substrate, an S element is introduced, N, P, S co-doping is realized, and the introduction of the hetero atoms improves the conductivity of the electrode material. And finally, repeatedly washing with water to remove impurities to obtain the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by the two-dimensional carbon nanosheets.
Compared with the prior art, the invention has the beneficial technical effects
1. The invention takes potassium sulfate as a sulfur source and a template, and adopts a simple green and environment-friendly process to prepare the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nano sheets for the zinc ion hybrid capacitor, thereby providing a general path for preparing the heteroatom-doped carbon anode material for the zinc ion hybrid capacitor with high area ratio capacitance;
2. according to the invention, by selecting the activating agent and the process, the use of strong alkali and strong acid substances is avoided, so that the risk of equipment corrosion is reduced, and the generation of subsequent waste liquid is reduced;
3. the product prepared by the invention has high specific surface area reaching 2265.8m2/g；
4. When the product prepared by the invention is used as a positive electrode material of a zinc ion mixed capacitor, the product shows high area specific capacitance and large energy density.
Drawings
Fig. 1 is a nitrogen adsorption and desorption isotherm of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon prepared from two-dimensional carbon nanosheets in embodiments 1, 2, and 3 of the present invention.
Fig. 2 is a field emission scanning electron microscope photograph of a three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, prepared in embodiment 2 of the present invention.
Fig. 3 is a N1s diagram of a three-dimensional nitrogen phosphorus sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, prepared in embodiment 2 of the present invention.
Fig. 4 is a P2P diagram of three-dimensional nitrogen phosphorus sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, prepared in example 2 of the present invention.
Fig. 5 is a S2p diagram of three-dimensional nitrogen phosphorus sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, prepared in example 2 of the present invention.
Fig. 6 is a graph of capacity of a zinc ion hybrid capacitor as a function of current density.
Fig. 7 is a graph of energy density as a function of power density for a zinc ion hybrid capacitor.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The reagent is purchased from Aladdin Biotechnology Ltd, and the main instruments and equipment used in the preparation and characterization of the carbon material are as follows: a field emission scanning electron microscope (S-4800, hitachi, japan), an X-ray photoelectron diffractometer (Thermo EBCALAB250, semer fly, usa), a specific surface area adsorption apparatus (ASAP2460, mike, usa), a blue-ray battery test system (CT3001A, mohniko gmbh), a tube furnace (OTF1200X, mixcrystal materials technology, inc.).
Example 1
The invention provides a specific preparation process of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, which comprises the following steps:
s1: preparation of nitrogen source and phosphorus source precursors: heating deionized water to 60 ℃, stirring at constant temperature, adding melamine, dissolving, slowly adding phytic acid, reacting for 6 hours, freezing, filtering and drying to obtain a nitrogen source and a phosphorus source precursor;
s2: pretreatment of reactants: grinding phenanthrene, potassium sulfate, oxalic acid and the product obtained in the step S1 according to a certain mass ratio, and uniformly mixing;
s3: and (5) transferring the reactant obtained in the step (S2) to a tube furnace, reacting under the protection of argon, allowing the reactant to be cooled to room temperature, and removing impurities to obtain the three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon constructed by the two-dimensional carbon nanosheets. Wherein the reaction condition is that the mixture is firstly heated to 98 ℃ at the speed of 2 ℃/min, the temperature is kept for 1h, then the mixture is heated to 850 ℃ at the speed of 5 ℃/min, and the mixture reacts for 30min at the temperature; the steps of removing impurities mainly comprise grinding, washing, drying, secondary grinding and sieving.
The mol ratio of melamine to phytic acid in S1 is 1: 1; the mass ratio of phenanthrene, potassium sulfate, potassium oxalate, nitrogen source and phosphorus source precursor in S2 is 1:0.5:2: 0.1.
The obtained three-dimensional honeycomb carbon constructed by two-dimensional carbon nano-sheets is named as NPS-HC2。
Example 2
The invention provides a specific preparation process of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, which comprises the following steps:
s1: preparation of nitrogen source and phosphorus source precursors: heating deionized water to 70 ℃, stirring at constant temperature, adding melamine, dissolving, slowly adding phytic acid, reacting for 9 hours, freezing, filtering and drying to obtain a nitrogen source and a phosphorus source precursor;
s2: pretreatment of reactants: grinding phenanthrene, potassium sulfate, an activating agent and the product obtained in the step S1 according to a certain mass ratio, and uniformly mixing;
s3: and (5) transferring the reactant obtained in the step (S2) to a tube furnace, reacting under the protection of argon, allowing the reactant to be cooled to room temperature, and removing impurities to obtain the three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon constructed by the two-dimensional carbon nanosheets. Wherein the reaction condition is that the mixture is firstly heated to 98 ℃ at the speed of 2 ℃/min, the temperature is kept for 1h, then the mixture is heated to 850 ℃ at the speed of 5 ℃/min, and the mixture reacts for 90min at the temperature; the steps of removing impurities mainly comprise grinding, washing, drying, secondary grinding and sieving.
The mol ratio of melamine to phytic acid in S1 is 2; the mass ratio of phenanthrene, potassium sulfate, potassium oxalate, nitrogen source and phosphorus source precursor in S2 is 1:1.2:3: 0.15.
The obtained three-dimensional honeycomb carbon constructed by two-dimensional carbon nano-sheets is named as NPS-HC3。
Example 3
The invention provides a specific preparation process of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets, which comprises the following steps:
s1: preparation of nitrogen source and phosphorus source precursors: heating deionized water to 80 ℃, stirring at constant temperature, adding melamine, dissolving, slowly adding phytic acid, reacting for 12 hours, freezing, filtering and drying to obtain a nitrogen source and a phosphorus source precursor;
s2: pretreatment of reactants: grinding phenanthrene, potassium sulfate, an activating agent and the product obtained in the step S1 according to a certain mass ratio, and uniformly mixing;
s3: and (5) transferring the reactant obtained in the step (S2) to a tube furnace, reacting under the protection of argon, allowing the reactant to be cooled to room temperature, and removing impurities to obtain the three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon constructed by the two-dimensional carbon nanosheets. Wherein the reaction condition is that the mixture is firstly heated to 98 ℃ at the speed of 2 ℃/min, the temperature is kept for 1h, then the mixture is heated to 900 ℃ at the speed of 5 ℃/min, and the mixture reacts for 150min at the temperature; the steps of removing impurities mainly comprise grinding, washing, drying, secondary grinding and sieving.
The mol ratio of melamine to phytic acid in S1 is 3; the mass ratio of phenanthrene, potassium sulfate, potassium oxalate, nitrogen source and phosphorus source precursor in S2 is 1:2:4: 0.3.
The obtained three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by two-dimensional carbon nanosheets is named as NPS-HC4。
The products prepared in examples 1 to 3 were used as test samples to determine pore structure parameters and elemental composition and content, respectively. The results are shown in tables 1 and 2:
TABLE 1 pore structure parameters of three-dimensional nitrogen, phosphorus, and sulfur doped cellular carbon constructed from two-dimensional carbon nanosheets
As shown in Table 1 and the results of FIG. 1, the specific surface area of the carbon material prepared by the invention is 1698.3-2265.8 m2The total pore volume is between 0.93 and 1.32cm3Between/g and containing a hydrocarbon thereinRich cellular structure for storing and transmitting electrolyte ions and electron conduction and a large number of defect sites generated by nitrogen, phosphorus and sulfur heteroatoms for ion adsorption, has high specific surface area reaching 2265.8m2/g。
Table 2 elemental composition and content of three-dimensional nitrogen phosphorus sulfur-doped honeycomb carbon constructed from two-dimensional carbon nanosheets
TABLE 2 As can be seen from FIGS. 2, 3, 4 and 5, NPS-HC3For example, the N, P, S contents were 3.45%, 1.65%, and 1.48%, respectively. In the preparation process, potassium sulfate is used as a sulfur source and a template, the doping of nitrogen, phosphorus and sulfur elements in a three-dimensional carbon material matrix can be realized in the space of a template limited domain, and a honeycomb structure with cavities is obtained in the carbon material matrix under the cutting action of an activator potassium oxalate, so that a large number of channels are provided for the transmission of ions and electrons.
The test methods in FIGS. 6 and 7 were performed by using zinc foil as the negative electrode, the prepared electrode material as the positive electrode, and 3mol/LZn (CF)3SO3)2The water solution is electrolyte, and the test voltage is 0.1-1.8V. Specific volume, energy density, and power density are calculated according to C ═ 2I ═ Vdt/3.6Vm, E ═ I ═ Vdt/3.6m, and P ═ 3600E/t, respectively. The test results of examples 1-3 are shown in Table 3.
TABLE 3 Zinc ion hybrid capacitor Performance
As can be seen from fig. 6, fig. 7 and table 3, the carbon material prepared by the present invention shows high area capacity and large energy density when applied to a zinc ion capacitor.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The preparation method of the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon is characterized by comprising the following steps of:
s1: preparation of Nitrogen and phosphorus precursors
Firstly, dissolving melamine in deionized water under the conditions of heating and stirring, then adding phytic acid, and after reaction, freezing, filtering and drying to obtain a nitrogen source and a phosphorus source precursor;
s2: pretreatment of reactants
Grinding phenanthrene, potassium sulfate, potassium oxalate and a nitrogen source and phosphorus source precursor in S1 and uniformly mixing;
s3: preparation of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon
And (5) transferring the reactant obtained in the step (S2) to a tubular furnace, reacting by taking argon as protective gas, and after the reaction is finished, cooling to room temperature to remove impurities to obtain the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon constructed by the two-dimensional carbon nanosheets.
2. The method for preparing the three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon according to claim 1, wherein the heating temperature in the S1 is 60-80 ℃, and the reaction time is 6-12 h.
3. The method for preparing three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon according to claim 1, wherein the molar ratio of melamine to phytic acid in S1 is 1: 1-3.
4. The preparation method of the three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon according to claim 1, wherein the mass ratio of phenanthrene, potassium sulfate, potassium oxalate, nitrogen source and phosphorus source precursor in S2 is 1:0.5-2:2-4: 0.1-0.3.
5. The method for preparing three-dimensional nitrogen, phosphorus and sulfur doped honeycomb carbon according to claim 1, wherein the reaction conditions in S3 are as follows: the flow rate of argon is 3-12mL/min, the temperature is 800-.
6. A three-dimensional nitrogen phosphorus sulfur doped carbon honeycomb prepared by the method of any one of claims 1 to 5.
7. Use of the three-dimensional nitrogen phosphorus sulfur doped honeycomb carbon of claim 6 in a zinc ion hybrid capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110517622.1A CN113948316B (en) | 2021-05-12 | 2021-05-12 | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110517622.1A CN113948316B (en) | 2021-05-12 | 2021-05-12 | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113948316A true CN113948316A (en) | 2022-01-18 |
| CN113948316B CN113948316B (en) | 2023-01-31 |
Family
ID=79327331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110517622.1A Active CN113948316B (en) | 2021-05-12 | 2021-05-12 | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113948316B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114496597A (en) * | 2022-02-23 | 2022-05-13 | 滁州学院 | Preparation method and application of electron-enhanced carbon nano-net |
| CN116313546A (en) * | 2023-03-15 | 2023-06-23 | 安徽理工大学 | Phosphorus doped honeycomb carbon material, preparation method and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170103113A (en) * | 2016-03-03 | 2017-09-13 | 성균관대학교산학협력단 | Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent |
| US10010866B1 (en) * | 2017-09-19 | 2018-07-03 | King Saud University | Nitrogen and phosphorus co-doped crystalline carbon materials |
| CN108584951A (en) * | 2018-06-27 | 2018-09-28 | 中国地质大学（武汉） | The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure |
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN109637831A (en) * | 2019-01-17 | 2019-04-16 | 中南大学 | A kind of preparation method of supercapacitor nitrogen-phosphor codoping porous carbon sheet |
| CN110155981A (en) * | 2019-05-23 | 2019-08-23 | 安徽工业大学 | A kind of preparation method of the supercapacitor porous charcoal nanometer sheet of nitrogen sulphur codope |
| CN111484013A (en) * | 2020-06-09 | 2020-08-04 | 安徽工业大学 | Preparation method of nitrogen-sulfur co-doped porous carbon for supercapacitor |
-
2021
- 2021-05-12 CN CN202110517622.1A patent/CN113948316B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170103113A (en) * | 2016-03-03 | 2017-09-13 | 성균관대학교산학협력단 | Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent |
| US10010866B1 (en) * | 2017-09-19 | 2018-07-03 | King Saud University | Nitrogen and phosphorus co-doped crystalline carbon materials |
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN108584951A (en) * | 2018-06-27 | 2018-09-28 | 中国地质大学（武汉） | The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure |
| CN109637831A (en) * | 2019-01-17 | 2019-04-16 | 中南大学 | A kind of preparation method of supercapacitor nitrogen-phosphor codoping porous carbon sheet |
| CN110155981A (en) * | 2019-05-23 | 2019-08-23 | 安徽工业大学 | A kind of preparation method of the supercapacitor porous charcoal nanometer sheet of nitrogen sulphur codope |
| CN111484013A (en) * | 2020-06-09 | 2020-08-04 | 安徽工业大学 | Preparation method of nitrogen-sulfur co-doped porous carbon for supercapacitor |
Non-Patent Citations (1)
| Title |
|---|
| YONGDE LONG: ""N, P, and S tri-doped holey carbon as an efficient electrocatalyst for oxygen reduction in whole pH range for fuel cell and zinc-air batteries"", 《CARBON》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114496597A (en) * | 2022-02-23 | 2022-05-13 | 滁州学院 | Preparation method and application of electron-enhanced carbon nano-net |
| CN114496597B (en) * | 2022-02-23 | 2024-05-28 | 滁州学院 | Preparation method and application of electronic reinforced carbon nano-network |
| CN116313546A (en) * | 2023-03-15 | 2023-06-23 | 安徽理工大学 | Phosphorus doped honeycomb carbon material, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113948316B (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111295359B (en) | Porous carbon, and positive electrode and lithium secondary battery comprising same | |
| JP5191483B2 (en) | Porous conductive carbon materials and their use | |
| CN108530073B (en) | Preparation method of flexible self-supporting three-dimensional porous graphene membrane | |
| CN113948316B (en) | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon | |
| CN108039465B (en) | Composite electrode material, preparation method and application thereof | |
| CN108630453B (en) | Method for preparing graphene-like carbon nanosheet material by one-step method and application of graphene-like carbon nanosheet material | |
| US20100189991A1 (en) | Macroporous carbon nanofoam composites and methods of making the same | |
| CN112086297B (en) | Graphene nanocarbon electrode material, preparation method and lithium ion capacitor electrode | |
| CN107161979B (en) | Carbon-based nanobelt porous material, and preparation method and application thereof | |
| CN106395802B (en) | Preparation method of graphene porous membrane | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| Cao et al. | Preparation of highly-active oxygen reduction reaction catalyst by direct co-pyrolysis of biomass with KOH | |
| CN113130880A (en) | Preparation method of positive electrode sulfur-fixing carrier material of lithium-sulfur battery | |
| CN111153403B (en) | Alginate-based porous carbon and preparation method and application thereof | |
| KR20180056099A (en) | Method for preparing high performance nanoporous graphene foams with versatile usages | |
| Bian et al. | N-doped graphitized porous carbon derived from N-rich polymer for improved supercapacitor performance | |
| CN112133571B (en) | Graphene cross-linked activated carbon composite membrane, preparation method and supercapacitor electrode | |
| CN110350201B (en) | Light high-conductivity graphene current collector for water-based battery and preparation method thereof | |
| CN110317005B (en) | Preparation method of graphene electrode material with three-dimensional hierarchical pore structure | |
| CN104826629A (en) | Synthetic method and applications of porous graphene composite catalyst | |
| CN113745510A (en) | Ordered porous hard carbon for sodium ion battery | |
| CN112201484A (en) | Two-dimensional ultrathin carbon nanosheet and preparation method and application thereof | |
| CN113880067B (en) | Preparation method of porous carbon super-structure material | |
| CN114496597B (en) | Preparation method and application of electronic reinforced carbon nano-network | |
| CN112117436B (en) | Novel two-dimensional carbon composite flexible electrode of sodium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 1, Huifeng West Road, Nanqiao District, Chuzhou, Anhui 239004 Applicant after: CHUZHOU University Address before: 239001 No.2 Langya West Road, Chuzhou City, Anhui Province Applicant before: CHUZHOU University |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |