CN110550630A - Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material - Google Patents
Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material Download PDFInfo
- Publication number
- CN110550630A CN110550630A CN201910939450.XA CN201910939450A CN110550630A CN 110550630 A CN110550630 A CN 110550630A CN 201910939450 A CN201910939450 A CN 201910939450A CN 110550630 A CN110550630 A CN 110550630A
- Authority
- CN
- China
- Prior art keywords
- phenanthrenequinone
- nitrogen
- ncnfws
- porous carbon
- composite material
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920000128 polypyrrole Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000005539 carbonized material Substances 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000011056 performance test Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000012512 characterization method Methods 0.000 abstract description 4
- 239000002121 nanofiber Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229920000557 Nafion® Polymers 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
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/372—Coating; Grafting; Microencapsulation
-
- 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
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method of a phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material. Physical characterization results show that the phenanthrenequinone functionalized nitrogen-doped porous carbon nanomaterial prepared by the invention has a mutually communicated nanofiber network structure, and phenanthrenequinone molecules are successfully modified on the surface of NCNFWs. Electrochemical performance tests show that the material shows excellent electrochemical capacitance performance and rate capability, and has good application prospect when being used as an electrode material of a super capacitor.
Description
Technical Field
the invention relates to preparation of a functionalized nitrogen-doped porous carbon nano material, in particular to preparation of a phenanthrenequinone functionalized nitrogen-doped porous carbon nano fiber network structure composite material; the invention also relates to application of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network composite material as an electrode material in a super capacitor, and belongs to the technical field of composite materials and the technical field of super capacitors.
Background
The super capacitor is a novel energy storage element with performance between the traditional capacitor and the secondary battery, is paid much attention to by researchers because of the fact that the super capacitor has energy density higher than the traditional capacitor and power density higher than the battery, and in addition, the super capacitor also has the characteristics of high charging and discharging efficiency, long cycle life, green, no pollution and the like, and therefore, the super capacitor is widely applied to a plurality of fields such as electric automobiles, aerospace and national defense science and technology. The super capacitor may be classified into an electric double layer capacitor (based on the formation of an electric double layer at the interface of an electrode material and an electrolyte solution to store electric charges) and a pseudo capacitor (based on the occurrence of a faraday redox process of an electrode active material during charge and discharge to store energy) according to its energy storage manner. As key factors determining the performance of the capacitor, the electrode materials mainly fall into the following categories: carbon materials, metal (hydr) oxides, conductive polymers and small organic molecules. The organic micromolecules with electrochemical active functional groups are rich in raw materials, belong to green and renewable energy sources, and exist in a natural state or can be synthesized in a laboratory; secondly, during the electrochemical cycle process, the organic molecules only have the oxygen-containing functional groups to perform reversible transformation, and the molecular structure is not damaged, which is the guarantee of obtaining good cycle stability. Compared with the traditional carbon materials, the carbon materials have electrochemical active functional groups, can realize multi-electron reversible Faraday reaction under low molecular weight, and lays a foundation for obtaining high energy density.
Disclosure of Invention
The invention aims to provide a preparation method of a phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material;
The invention aims to research the electrochemical capacitance performance of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material, and the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material is expected to be used as a supercapacitor electrode material.
Preparation of phenanthrenequinone functionalized porous carbon nanofiber network structure composite material
The preparation method of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material comprises the following steps:
(1) Adding polypyrrole powder and an activator KOH into secondary water according to the mass ratio of 1:1 ~ 1:3, stirring for 10 ~ 12 hours at room temperature, drying an activated product, carbonizing and activating for 1 ~ 2 hours at the temperature of 750-850 ℃ under the protection of nitrogen, cooling, washing for multiple times by using dilute hydrochloric acid and the secondary water until the product is neutral, and drying to obtain a nitrogen-doped carbon material precursor which is marked as NCNFWs;
(2) And (3) phenanthrenequinone functionalization of the nitrogen-doped carbon material, namely dissolving phenanthrenequinone in N, N-dimethylformamide solution, adding the prepared nitrogen-doped carbon material precursor NCNFWs, carrying out ultrasonic treatment for 0.5 ~ 1h, then reacting for 10 ~ 12h at 160 ~ 180 ℃ and 180 ℃, repeatedly washing a product with secondary water, and carrying out vacuum drying at 60 ~ 80 ℃ to obtain the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material which is marked as PQ-NCNFWs.
The dosage of the phenanthrenequinone is 0.2 ~ 1 times of the mass of the nitrogen-doped carbonized material.
Physical characterization of phenanthrenequinone functionalized porous carbon nanofiber network structure composite material
1. Field emission scanning electron microscope (FE-SEM)
Fig. 1 is a field emission scanning electron microscope (FE-SEM) image of the nitrogen-doped porous carbon nanofiber network (NCNFWs) prepared by the present invention, and it can be seen from fig. 1 that the NCNFWs are all interconnected nanofiber network structures. Fig. 2 is a field emission scanning electron microscope (FE-SEM) image of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network (PQ-NCNFWs) composite material prepared by the present invention, and it can be seen that the structure of NCNFWs is not changed after phenanthrenequinone non-covalent functionalization, and the existence of crystals is not observed in the image, which indicates that phenanthrenequinone is adsorbed on the surface of carbon nanofibers in a molecular form.
2. Infrared spectrogram (FT-IR)
FIG. 3 is an infrared spectrum (FT-IR) of PQ, NCNFWs and PQ-NCNFWs. As can be seen from FIG. 3, the absorption peaks of PQ and NCNFWs are shown in the spectrum of the PQ-NCNFWs composite material, and the peak positions are basically consistent but slightly deviated, which indicates that a stronger pi-pi interaction exists between PQ and NCNFWs, and indicates that the phenanthrenequinone molecule is successfully modified on the surface of the NCNFWs.
Third, electrochemical performance
the electrochemical performance characterization of the phenanthrenequinone functionalized nitrogen doped porous carbon nanofiber network (PQ-NCNFWs) composite material prepared by the invention is described in detail by an electrochemical workstation CHI 760E.
1. Preparing the electrode of the super capacitor: a total of 4.7 mg of mixed solid powder of PQ-NCNFWs composite material and acetylene black (the mass percentages of PQ-NCNFWs and acetylene black are 85% and 15%, respectively) was taken, 0.4 ml of 0.25 wt% Nafion solution was added thereto, and ultrasonic dispersion was carried out to form a suspension. Then 6. mu.L of the suspension was dropped on the surface of a glassy carbon electrode by using a pipette gun, and the suspension was dried at room temperature and used for testing.
2. Electrochemical performance test
the prepared motor is used as a working electrode, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to form a three-electrode system, 1mol of L -1 H 2 SO 4 solution is used as an electrolyte solution, and electrochemical performance test is carried out under a potential window of-0.3-0.7V.
FIG. 4 is a plot of cyclic voltammetry for NCNFWs and PQ-NCNFWs at a scan rate of 10mV s -1 in 1mol of L -1 H 2 SO 4 electrolyte solution from which it can be seen that the cyclic voltammetry of NCNFWs is approximately rectangular, reflecting its typical electrical double layer energy storage mechanism, while the PQ-NCNFWs composite exhibits a pair of very distinct redox peaks based on the cyclic voltammetry of NCNFWs, resulting from the redox reaction of PQ, indicating the successful adsorption of PQ molecules to the surface of NCWNFs.
FIG. 5 is a constant current charge and discharge diagram of NCNFWs and PQ-NCNFWs at a current density of 1A g -1 in 1mol of L -1 H 2 SO 4 electrolyte solution from which it is apparent that the two electrode materials have different energy storage mechanisms.
FIG. 6 is a cycle curve of PQ-NCNFWs at different scanning rates, wherein the curve has a pair of very distinct redox peaks, and the oxidation peak and the reduction peak show very good symmetry, which indicates that the electrochemical reaction of PQ molecule has very good kinetic reversibility. As the scan rate increased, the shape of the CV curve remained substantially unchanged, indicating that the material had very excellent rate capability and a fast current-potential response.
FIG. 7 is a constant current charge-discharge curve of PQ-NCNFWs at different current densities, and the specific capacitance of the material is 404.8, 382.8, 373.8, 364.5, 359.1 and 354Fg -1 when the current densities are 1, 2, 3, 5, 7 and 10A g -1 respectively, and the capacitance of the material is kept 87.45% under 1A g -1 when the current density is 10A g -1, which shows that PQ-NCNFWs has higher specific capacitance and excellent double capacitance rate, has the potential of being used as an electrode material of a super capacitor, and is consistent with the result of cyclic voltammetry curve test.
FIG. 8 is a Nyquist curve of the PQ-NCNFWs composite material, the frequency range is 0.01 Hz ~ 100 kHz, it can be seen that the high frequency region of the impedance spectrum has an obvious semicircle, the intercept between the semicircle and the real axis represents the equivalent series internal resistance, and the characteristic that the curve is nearly parallel to the imaginary axis in the low frequency region indicates that the composite material has good capacitance characteristics.
in conclusion, the special network structure of the polypyrrole nano-fiber network structure prepared by the invention provides a smooth path for the continuous permeation and transmission of electrolyte ions, and the nitrogen-doped porous carbon material obtained by activation and carbonization not only maintains the original morphological characteristics, but also has a larger specific surface area and more abundant ion transmission channels. Organic micromolecule phenanthrenequinone with a conjugated structure is fixed on the surface of the nitrogen-doped porous carbon nanofiber through a non-covalent functionalization strategy to obtain a phenanthrenequinone modified composite material, the composite material simultaneously reflects the Faraday pseudocapacitance effect of the organic micromolecules and the electric double layer capacitance effect of the carbon material, and the superposition of the electric double layer capacitance and the electrochemical capacitance is generated, so that larger specific capacitance is provided. The method provides a feasible research scheme for novel energy storage materials, and also provides a novel platform for the design and performance optimization of the electrode material of the super capacitor.
drawings
Fig. 1 is a field emission scanning electron microscope image of nitrogen-doped porous carbon nanofiber network (NCNFWs).
FIG. 2 is a scanning electron microscope image of the field emission of the PQ-NCNFWs composite material prepared by the present invention.
FIG. 3 is an infrared spectrum of NCNFWs, PQ and PQ-NCNFWs composites.
FIG. 4 is a plot of cyclic voltammograms for NCNFWs and PQ-NCNFWs composite electrodes at a scan rate of 10mV s -1 in 1mol of L -1 H 2 SO 4 electrolyte solution.
FIG. 5 is a constant current charge-discharge diagram of the NCNFWs and PQ-NCNFWs composite electrode at a current density of 1A g -1 in 1mol of L -1 H 2 SO 4 electrolyte solution.
FIG. 6 is a plot of cyclic voltammograms of PQ-NCNFWs composite electrodes at different scan rates in 1mol of L -1 H 2 SO 4 electrolyte solution.
FIG. 7 is a constant current charge and discharge curve diagram of PQ-NCNFWs composite electrode in 1mol of L -1 H 2 SO 4 electrolyte solution under different current densities.
FIG. 8 is a graph of the AC impedance of a PQ-NCNFWs composite electrode.
Detailed Description
The preparation of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network (PQ-NCNFWs) composite material and the preparation and electrochemical properties of the electrode material thereof are further described in detail by specific examples.
Instruments and reagents used: CHI760E electrochemical workstation (shanghai chenhua instruments) was used for electrochemical performance testing; an electronic balance (beijing sidoris instruments ltd) for weighing the medicine; a constant temperature magnetic stirrer (90-1 Shanghai province of analytical instruments); a tube furnace (GSL-1700X Combined fertilizer Crystal Material technology Co., Ltd.); an electric hot blast drying oven (101A-1 Shanghai laboratory Instrument plant, Inc.); field emission scanning electron microscopy (Ultra Plus, Carl Zeiss, Germany) was used for the morphological characterization of materials; FTS3000 Fourier Infrared Spectroscopy (DIGILAB, USA) to analyze composition; pyrrole (Shanghai Aladdin Biotechnology, Inc.); phenanthrenequinone (Shanghai Michelin Biochemical technology, Inc.); potassium hydroxide (national chemical group, chemical Co., Ltd.). The water used in the experiment process is secondary water, and the reagents used in the experiment are analytically pure.
Example one
1. Preparation of PQ-NCNFWs-1 composite:
(1) Preparing polypyrrole, namely dissolving 7.3g of hexadecyl trimethyl ammonium bromide in 120mL of hydrochloric acid solution with the concentration of 1mol ∙ L -1 under the ice bath condition, then adding 13.7g of ammonium persulfate, magnetically stirring for 30min, dropwise adding 8.3mL of pyrrole monomer into the solution, continuously stirring for 24h under the ice bath condition, filtering and separating precipitates, washing the precipitates for multiple times by using secondary water and absolute ethyl alcohol, and drying the solids at 60 ℃ in vacuum to obtain black polypyrrole powder;
(2) Adding 0.5g of polypyrrole powder and 1g of KOH into 20mL of secondary water, stirring at room temperature overnight, drying at 80 ℃, putting the obtained solid into a tubular furnace, activating and carbonizing at 800 ℃ for 1h under the protection of nitrogen, washing with 1mol of HCl -1 and the secondary water for multiple times after cooling until the solid is neutral, and finally drying in vacuum at 80 ℃ for 12h to obtain the NCNFWs material;
(3) Weighing 0.02g of phenanthrenequinone, dissolving in 60mL of N, N-dimethylformamide solution, adding 0.1g of NCNFWs, carrying out ultrasonic treatment for 0.5h, reacting at 180 ℃ for 12h, repeatedly washing a product with secondary water, and carrying out vacuum drying at 60 ℃ to obtain the PQ-NCNFWs-1 composite material.
2. Preparing a PQ-NCNFWs-1 composite material electrode: fully grinding 4 mg of PQ-NCNFWs-1 and 0.7 mg of acetylene black (the mass ratio is 85: 15) in a mortar uniformly, then adding 0.4 ml of 0.25 wt% Nafion solution into the mixed powder, and performing ultrasonic dispersion to form a suspension; then 6. mu.L of the suspension was dropped on the surface of a glassy carbon electrode by using a pipette gun, and the suspension was dried at room temperature and used for testing.
3. And (2) performing electrochemical performance test by taking the PQ-NCNFWs-1 composite material electrode as a working electrode and taking a carbon rod and a saturated calomel electrode as a counter electrode and a reference electrode respectively, and performing electrochemical performance test under a potential window of-0.3-0.7V by taking 1mol of L -1 H 2 SO 4 solution as an electrolyte solution, wherein the specific capacitance of the electrode material can reach 288.6Fg -1 when the current density is 1A g -1.
Example 2
1. Preparation of PQ-NCNFWs-2 composite:
The preparation and the activation carbonization of the polypyrrole are the same as the example 1;
preparation of PQ-NCNFWs-2: weighing 0.04g of phenanthrenequinone, dissolving in 60mL of N, N-dimethylformamide solution, adding 0.1g of NCNFWs, carrying out ultrasonic treatment for 0.5h, reacting at 180 ℃ for 12h, repeatedly washing a product with secondary water, and carrying out vacuum drying at 60 ℃ to obtain the PQ-NCNFWs-2 composite material.
2. The PQ-NCNFWs-2 composite electrode was prepared as in example 1;
3. The electrochemical performance test is the same as that of the embodiment 1, and the test result shows that when the current density is 1A g -1, the specific capacitance of the electrode material can reach 404.8Fg -1.
Example 3
1. Preparation of PQ-NCNFWs-3 composite:
The preparation and the activation carbonization of the polypyrrole are the same as the example 1;
Preparation of PQ-NCNFWs-3: weighing 0.1g of phenanthrenequinone, dissolving in 60mL of N, N-dimethylformamide solution, adding 0.1g of NCNFWs, carrying out ultrasonic treatment for 0.5h, reacting at 180 ℃ for 12h, repeatedly washing a product with secondary water, and carrying out vacuum drying at 60 ℃ to obtain the PQ-NCNFWs-3 composite material.
2. The PQ-NCNFWs-3 composite electrode was prepared as in example 1;
3. The electrochemical performance test is the same as that of the embodiment 1, and the detection result is that when the current density is 1A g -1, the specific capacitance of the electrode material can reach 219.7F g -1.
Claims (3)
1. a preparation method of a phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material comprises the following steps:
(1) Adding polypyrrole powder and an activator KOH into secondary water according to the mass ratio of 1:1 ~ 1:3, stirring for 10 ~ 12 hours at room temperature, drying an activated product, carbonizing and activating for 1 ~ 2 hours at 750 ~ 850 ℃ under the protection of nitrogen, cooling, washing with diluted hydrochloric acid and the secondary water for multiple times until the product is neutral, and drying to obtain the nitrogen-doped carbonized material;
(2) And (3) phenanthrenequinone functionalization of the nitrogen-doped carbonized material, namely dissolving phenanthrenequinone in N, N-dimethylformamide solution, adding the prepared nitrogen-doped carbonized material NCNFWs, carrying out ultrasonic treatment for 0.5 ~ 1h, then reacting for 10 ~ 12h at 160 ~ 180 ℃ under 180 ℃, repeatedly washing a product with secondary water, and carrying out vacuum drying at 60 ~ 80 ℃ to obtain the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material.
2. The method for preparing the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material as claimed in claim 1, wherein the dosage of the phenanthrenequinone is 0.2 ~ 1 times of the mass of the nitrogen-doped carbon material.
3. The application of the phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material prepared by the method of claim 1 as a supercapacitor electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910939450.XA CN110550630A (en) | 2019-09-30 | 2019-09-30 | Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910939450.XA CN110550630A (en) | 2019-09-30 | 2019-09-30 | Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110550630A true CN110550630A (en) | 2019-12-10 |
Family
ID=68742077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910939450.XA Pending CN110550630A (en) | 2019-09-30 | 2019-09-30 | Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110550630A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113206229A (en) * | 2021-04-22 | 2021-08-03 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of quinone @ nitrogen-doped microporous carbon composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN103700818A (en) * | 2013-12-20 | 2014-04-02 | 复旦大学 | Sulfur-carbon composite material with nitrogen-doped porous carbon nanofiber net-shaped structure, as well as preparation method and application of composite material |
| KR101448211B1 (en) * | 2013-09-02 | 2014-10-08 | 한국과학기술원 | Nitrogen-Doped Porous Carbon Materials and Method of Manufacturing the Same |
| CN105293472A (en) * | 2015-11-24 | 2016-02-03 | 绍兴文理学院 | Preparation method of strong acidic ionic liquid functionalized nano porous carbon material |
| CN109019596A (en) * | 2018-07-16 | 2018-12-18 | 西北师范大学 | The preparation and application of one organic molecular species non-covalent bond functionalization biomass carbon material |
-
2019
- 2019-09-30 CN CN201910939450.XA patent/CN110550630A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| KR101448211B1 (en) * | 2013-09-02 | 2014-10-08 | 한국과학기술원 | Nitrogen-Doped Porous Carbon Materials and Method of Manufacturing the Same |
| CN103700818A (en) * | 2013-12-20 | 2014-04-02 | 复旦大学 | Sulfur-carbon composite material with nitrogen-doped porous carbon nanofiber net-shaped structure, as well as preparation method and application of composite material |
| CN105293472A (en) * | 2015-11-24 | 2016-02-03 | 绍兴文理学院 | Preparation method of strong acidic ionic liquid functionalized nano porous carbon material |
| CN109019596A (en) * | 2018-07-16 | 2018-12-18 | 西北师范大学 | The preparation and application of one organic molecular species non-covalent bond functionalization biomass carbon material |
Non-Patent Citations (5)
| Title |
|---|
| DANIELA M. ANJOS ET AL.: ""Pseudocapacitance and performance stability of quinone-coated carbon onions"", 《NANO ENERGY》 * |
| QIE, LONG ET AL.: ""Nitrogen‐Doped Porous Carbon Nanofiber Webs as Anodes for Lithium Ion Batteries with a Superhigh Capacity and Rate Capability"", 《ADVANCED MATERIALS》 * |
| WENBIN WANG ET AL.: ""Nitrogen-doped hollow carbon spheres functionalized by 9,10-phenanthrenequinone molecules as a high-performance electrode for asymmetric supercapacitors"", 《NEW JOURNAL OF CHEMISTRY》 * |
| YAO LI ET AL.: ""Nitrogen-doped porous carbon nano fiber webs for efficient CO2 capture and conversion"", 《CARBON》 * |
| ZHOU, LAN ET AL.: ""Nitrogen-doped porous carbon nanofiber webs/sulfur composites as cathode materials for lithium-sulfur batteries"", 《ELECTROCHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113206229A (en) * | 2021-04-22 | 2021-08-03 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of quinone @ nitrogen-doped microporous carbon composite material |
| CN113206229B (en) * | 2021-04-22 | 2024-03-19 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of quinone@nitrogen doped microporous carbon composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Synthesis and pseudocapacitive studies of composite films of polyaniline and manganese oxide nanoparticles | |
| Wu et al. | Core–shell nanospherical polypyrrole/graphene oxide composites for high performance supercapacitors | |
| Yang et al. | Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor | |
| Chen et al. | Polypyrrole Shell@ 3D‐Ni metal core structured electrodes for high‐performance supercapacitors | |
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| Tian et al. | Growth of polyaniline thorns on hybrid electrospun CNFs with nickel nanoparticles and graphene nanosheets as binder-free electrodes for high-performance supercapacitors | |
| CN111118883B (en) | Cellulose-based carbon nanofiber composite material and preparation and application thereof | |
| CN102543464A (en) | ZnO/reduced graphene oxide/polypyrrole ternary composite material preparation method, and application of the ternary composite material | |
| Jiang et al. | One-pot mechanochemical exfoliation of graphite and in situ polymerization of aniline for the production of graphene/polyaniline composites for high-performance supercapacitors | |
| CN109950058B (en) | Porous carbon material based on porous organic polymer structure and preparation method and application thereof | |
| Zeng et al. | Nitrogen-doped hierarchical porous carbon for supercapacitor with well electrochemical performances | |
| Yang et al. | Graphene covalently functionalized with 2, 6-diaminoanthraquinone (DQ) as a high performance electrode material for supercapacitors | |
| CN109167043A (en) | Solvent heat chain polymerization method prepares macromolecule combination electrode material | |
| Xu et al. | Facile hydrothermal synthesis of tubular kapok fiber/MnO 2 composites and application in supercapacitors | |
| CN110854381B (en) | Preparation method of carbon-doped tin-manganese composite oxide nanofiber modified by cobalt oxide | |
| Qin et al. | Ni-MOF composite polypyrrole applied to supercapacitor energy storage | |
| Gao et al. | Core-shell Ppy@ N-doped porous carbon nanofiber-based electrodes for high-property supercapacitors | |
| Khan et al. | Tailoring performance of hybrid supercapacitors by fluorine-rich block copolymer-derived carbon coated mixed-phase TiO2 nanoparticles | |
| Zhang et al. | 2, 6-Diaminopyridine decorated reduced graphene oxide as integrated electrode with excellent electrochemical properties for aqueous supercapacitors | |
| Shi et al. | N/S co-doped carbon nanosheets derived from sugarcane processing by-products for flexible solid-state supercapacitors | |
| CN110550630A (en) | Preparation and application of phenanthrenequinone functionalized nitrogen-doped porous carbon nanofiber network structure composite material | |
| CN112646181A (en) | Polyimide-based organic polymer cathode material polymerized in situ and preparation method thereof | |
| Xie et al. | Preparation of cotton-shaped CNT/PANI composite and its electrochemical performances | |
| CN109019596A (en) | The preparation and application of one organic molecular species non-covalent bond functionalization biomass carbon material | |
| Dai et al. | Structure, morphology and energy storage properties of imide conjugated microporous polymers with different cores and the corresponding composites with CNT |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191210 |