CN115394562A - Nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and preparation method thereof - Google Patents
Nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007772 electrode material Substances 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 241001388119 Anisotremus surinamensis Species 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000004793 Polystyrene Substances 0.000 claims description 38
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- 229920002223 polystyrene Polymers 0.000 claims description 38
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 38
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- POAVHXRSAJTSTD-UHFFFAOYSA-N 1-[(4-ethenylphenyl)methyl]pyrrolidine Chemical compound C1=CC(C=C)=CC=C1CN1CCCC1 POAVHXRSAJTSTD-UHFFFAOYSA-N 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 15
- 239000004005 microsphere Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000012312 sodium hydride Substances 0.000 claims description 9
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 15
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003990 capacitor Substances 0.000 abstract description 9
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
Abstract
The invention relates to the technical field of super capacitors and discloses a nitrogen-doped porous carbon loaded pompon NiO composite electrode material, compared with pure porous carbon and nickel oxide electrode materials, the composite electrode material has better conductivity and specific capacitance, and the porous carbon and nickel oxide in the composite material generate synergistic effect, so that the electrochemical performance of the composite electrode material is improved.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and a preparation method thereof.
Background
With the rapid development of human civilization, the demand for energy has increased exponentially, and the main source of energy at present is the combustion of fossil fuel, but the irreversible combustion of fossil fuel generates greenhouse gases, thereby causing environmental deterioration, and therefore, the search for eco-friendly and cost-effective energy is an urgent requirement for human being to continue to live on this planet, and solar energy and wind energy may be possible energy solutions in the future, but both resources are not always available on demand, and therefore, there is an urgent need for a rapidly-charged energy storage device that can store electric energy for future use, and an ultracapacitor, which is considered as an advanced hybrid energy storage system due to its high power density, long-term cycle stability, high safety and environmental friendliness, but in addition to which specific capacity is a major problem of the ultracapacitor, which is very low compared to rechargeable batteries, and therefore, most considerable research efforts are focused on increasing the specific capacity of the ultracapacitor through an electrical structuring strategy or through material engineering.
Electrochemical capacitors can be divided into two types based on energy storage mechanisms: an Electric Double Layer Capacitor (EDLC) and a dummy capacitor, the dummy capacitor may provide a high capacitance 3-4 times by using a rapid reversible oxidation-reduction reaction of a surface or a near-surface, as compared to an electric double layer capacitor that stores energy only by ion adsorption/desorption of a surface of an electrode material, and one of major factors affecting the dummy capacitor is an electrode material, transition metal oxides such as manganese oxide, cobalt oxide, nickel oxide and iron oxide, which are typical dummy capacitance electrode materials, wherein, due to various oxidation states of NiO, low cost and theoretically high specific capacitance, more and more attention has been drawn in recent years, but NiO as an electrode material has poor conductivity, is susceptible to a volume expansion effect during charge and discharge, has poor stability, low actual specific capacitance, and as a typical electrode, the porous carbon material has advantages of low cost and strong conductivity, and its pore structure and large specific surface area may provide more contact sites for an electrolyte, but the theoretical specific capacitance of the porous carbon is low, and as an electrode material alone, the storage capacity of the capacitor is poor.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and a preparation method thereof, which solve the problems of low conductivity of the NiO electrode material and specific capacity difference of the porous carbon electrode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material comprises the following steps:
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinylbenzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent, adding tetramethylethylenediamine and n-butyllithium into the hexane solvent for polymerization, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrolyl polystyrene;
(3) Completely dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, ultrasonically dispersing uniformly, then adding aluminum chloride for crosslinking reaction, after the reaction is finished, filtering and washing by using ethanol to obtain pyrrolyl polystyrene crosslinked microspheres coated with the nano-silica;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinked microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) Dissolving nickel nitrate, urea and porous carbon in deionized water, uniformly stirring, transferring to a reaction kettle for hydrothermal reaction, and after the reaction is finished, filtering, washing and drying to obtain the nitrogen-doped porous carbon loaded pompon NiO composite electrode material.
Preferably, in the step (2), the mass ratio of styrene to 1- (4-vinylbenzyl) pyrrolidine to tetramethylethylenediamine to n-butyllithium is (100).
Preferably, the polymerization reaction in the step (2) has a reaction temperature of 50-80 ℃ and a reaction time of 2-3h.
Preferably, in the step (3), the mass ratio of the pyrrolyl polystyrene, the carbon tetrachloride, the nano silica and the aluminum chloride is 100-800-1200.
Preferably, the reaction temperature of the crosslinking reaction in the step (3) is 75-90 ℃, and the reaction time is 18-36h.
Preferably, the carbonization temperature in the step (4) is 580-650 ℃, and the carbonization time is 2-4h.
Preferably, in the step (5), the mass ratio of the nickel nitrate to the urea to the nitrogen-doped porous carbon is 25-40.
Preferably, the reaction temperature of the hydrothermal reaction in the step (5) is 100-125 ℃, and the reaction time is 5-10h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
according to the nitrogen-doped porous carbon loaded pompon NiO composite electrode material, tetramethylethylenediamine is used as a regulator, n-butyl lithium is used as an initiator, so that 1- (4-vinylbenzyl) pyrrolidine and styrene are subjected to a polymerization reaction in a hexane solvent to obtain pyrrolyl polystyrene, then nano silicon dioxide is used as a pore-making template agent, polystyrene is used as a carbon source, pyrrolyl is used as a nitrogen source, carbon tetrachloride is used as a cross-linking agent, aluminum chloride is used as a catalyst, so that the pyrrolyl polystyrene can be subjected to a cross-linking reaction firstly, nano silicon dioxide is coated on pyrrolyl polystyrene cross-linked microspheres, then the nano silicon dioxide coated on the pyrrolyl polystyrene cross-linked microspheres is carbonized, hydrofluoric acid is used for removing the nano silicon dioxide, nitrogen-doped porous carbon is obtained, finally, the nitrogen-doped porous carbon is used as a carrier, nickel nitrate is used as a nickel source, and urea is used as a precipitator, so that the nitrogen-doped porous carbon loaded pompon NiO composite electrode material is obtained.
Compared with pure porous carbon and nickel oxide electrode materials, the composite electrode material has more excellent conductivity and specific capacitance, the porous carbon and nickel oxide in the composite material generate a synergistic effect, the electrochemical performance of the composite electrode material is improved, wherein the nickel oxide is loaded on the nitrogen-doped porous carbon, the specific capacitance of the porous carbon is increased, and when the composite electrode material is subjected to an electrochemical test, OH (hydroxyl) is added - Rapidly carrying out oxidation-reduction reaction with the composite electrode material and the electrolyte solution, wherein the porous carbon material has a porous structure of OH - The rapid transmission channel is provided, the diffusion efficiency of ions in an electrolyte solution is improved, the use efficiency of nickel oxide is improved, in addition, the porous carbon has good conductivity, the porous carbon is added into the composite electrode material, the conductivity of the composite material can be improved, the stability of capacitance is kept, when the nickel oxide grows in situ in the porous carbon material, the porous carbon not only allows the nickel oxide to pass through growth sites, but also limits the growth particle size of the nickel oxide, so that the particle size of the nickel oxide is smaller, the smaller nickel oxide has larger specific surface area, the probability of contact between the nickel oxide and the electrolyte is increased, meanwhile, more active sites are exposed, and the electrochemical efficiency of the nickel oxide is improved, and the porous structure limits the expansion effect of the nickel oxide electrode in the using process, and avoids the problem of unstable electrode capacitance caused by the powdering of the electrode material, the porous structure and the pompon-shaped structure endow the electrode material with larger specific surface area, so that the electrolyte is more fully contacted with the electrolyte material, the transmission distance of ions in the electrolyte is further shortened, the use efficiency of the composite electrode material is improved, the nitrogen-doped porous carbon can increase the hydrophilicity of the porous carbon material, the surface wettability of the electrode material is improved, the diffusion resistance of the ions is reduced, the electrolyte is further contacted with the composite electrode material, and the nitrogen element can activate adjacent carbon atoms, so that the rapid transmission of the ions between the porous carbon is promoted, and the electrolytic material is attractedIons in the electrolyte increase the capacitance characteristic of double capacitance, and meanwhile, nitrogen atoms can increase the pseudo capacitance of the composite electrode material, so that the capacitance of the composite electrode battery is improved.
Drawings
FIG. 1 is a reaction scheme of 1- (4-vinylbenzyl) pyrrolidine with styrene.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a nitrogen-doped porous carbon-loaded pompon NiO composite electrode material comprises the following steps:
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) According to the mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of pyrrolyl polystyrene to carbon tetrachloride to nano-silica to aluminum chloride is 100-800-180-80, the reaction temperature is 75-90 ℃, the reaction time is 18-36h, and after the reaction is finished, filtering and washing with ethanol to obtain pyrrolyl polystyrene crosslinking microspheres coated with nano-silica;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinked microspheres into a tubular furnace, carbonizing at 580-650 ℃ for 2-4h in the nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) According to the following steps of 25-40.
Example 1
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of pyrrolyl polystyrene to carbon tetrachloride to nano-silica to aluminum chloride is 100;
(4) Putting the nanometer silicon dioxide coated with the pyrrole-based polystyrene crosslinked microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, wherein the carbonization temperature is 580 ℃, the carbonization time is 2 hours, and then respectively washing and drying by using hydrofluoric acid solution and deionized water to obtain nitrogen-doped porous carbon;
(5) According to the preparation method, the preparation method comprises the following steps of (1) dissolving nickel nitrate, urea and porous carbon in deionized water according to the ratio of 25.
Example 2
(1) Will be provided withDissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinylbenzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano-silica to the aluminum chloride is 100 to 65, the reaction temperature is 80 ℃, and the reaction time is 24h, and after the reaction is finished, filtering and washing with ethanol to obtain pyrrolyl polystyrene crosslinking microsphere coated nano-silica;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinking microspheres into a tubular furnace, carbonizing at 600 ℃ for 2.5h in the nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) According to the method, the preparation method comprises the following steps of dissolving nickel nitrate, urea and porous carbon in deionized water according to the ratio of 30.
Example 3
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinylbenzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of pyrrolyl polystyrene to carbon tetrachloride to nano-silica to aluminum chloride is 100;
(4) Putting the nanometer silicon dioxide coated with the pyrrole-based polystyrene crosslinked microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, wherein the carbonizing temperature is 610 ℃ and the carbonizing time is 3h, and then respectively washing and drying by using hydrofluoric acid solution and deionized water to obtain nitrogen-doped porous carbon;
(5) According to the preparation method, nickel nitrate, urea and porous carbon are dissolved in deionized water according to the proportion of 20.
Example 4
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of pyrrolyl polystyrene to carbon tetrachloride to nano-silica to aluminum chloride is 1100;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinking microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere at 620 ℃ for 3h, respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) According to 35.
Example 5
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of pyrrolyl polystyrene to carbon tetrachloride to nano-silica to aluminum chloride is 100;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinking microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, wherein the carbonizing temperature is 650 ℃, the carbonizing time is 4 hours, then respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) According to the preparation method, nickel nitrate, urea and porous carbon are dissolved in deionized water according to the proportion of 40.
Comparative example 1
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinylbenzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano-silica, and after uniform ultrasonic dispersion, adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano-silica to the aluminum chloride is 100;
(4) Putting the nanometer silicon dioxide coated with the pyrrole-based polystyrene crosslinked microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, wherein the carbonizing temperature is 480 ℃ and the carbonizing time is 1.4h, and then respectively washing and drying by using hydrofluoric acid solution and deionized water to obtain nitrogen-doped porous carbon;
(5) According to the method, the preparation method comprises the following steps of (1) dissolving nickel nitrate, urea and porous carbon in deionized water according to the ratio of 18.
The composite electrode material is subjected to electrochemical test by using a three-electrode system, an electrochemical workstation is an RST series, the composite electrode material, acetylene black and polytetrafluoroethylene are mixed and ground according to the mass ratio of 8.5.
Claims (8)
1. The utility model provides a nitrogen doping porous carbon load pompon NiO combined electrode material which characterized in that: the preparation method of the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material comprises the following steps:
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinylbenzyl) pyrrolidine with molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent, adding tetramethylethylenediamine and n-butyllithium into the hexane solvent, carrying out polymerization reaction, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrolyl polystyrene;
(3) Completely dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, performing ultrasonic dispersion uniformly, then adding aluminum chloride for crosslinking reaction, and after the reaction is finished, obtaining pyrrolyl polystyrene crosslinked microspheres coated with nano silicon dioxide;
(4) Putting the nanometer silicon dioxide coated with the pyrrolyl polystyrene crosslinked microspheres into a tubular furnace, carbonizing in a nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) Dissolving nickel nitrate, urea and porous carbon in deionized water, uniformly stirring, transferring to a reaction kettle for hydrothermal reaction, and after the reaction is finished, filtering, washing and drying to obtain the nitrogen-doped porous carbon loaded pompon NiO composite electrode material.
2. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: in the step (2), the mass ratio of styrene to 1- (4-vinylbenzyl) pyrrolidine to tetramethylethylenediamine to n-butyllithium is (100).
3. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: the reaction temperature of the polymerization reaction in the step (2) is 50-80 ℃, and the reaction time is 2-3h.
4. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: in the step (3), the mass ratio of the pyrrolyl polystyrene, the carbon tetrachloride, the nano silicon dioxide and the aluminum chloride is 100-800-1200.
5. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: the reaction temperature of the crosslinking reaction in the step (3) is 75-90 ℃, and the reaction time is 18-36h.
6. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: the carbonization temperature in the step (4) is 580-650 ℃, and the carbonization time is 2-4h.
7. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: in the step (5), the mass ratio of nickel nitrate, urea and nitrogen-doped porous carbon is (25-40).
8. The nitrogen-doped porous carbon-supported pompon NiO composite electrode material of claim 1, which is characterized in that: the reaction temperature of the hydrothermal reaction in the step (5) is 100-125 ℃, and the reaction time is 5-10h.
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