CN115394562B - 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 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 239000007772 electrode material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 241001388119 Anisotremus surinamensis Species 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000004793 Polystyrene Substances 0.000 claims description 50
- 229920002223 polystyrene Polymers 0.000 claims description 50
- 239000005543 nano-size silicon particle Substances 0.000 claims description 40
- 235000012239 silicon dioxide Nutrition 0.000 claims description 40
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 34
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 32
- 238000004132 cross linking Methods 0.000 claims description 30
- 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 26
- 238000005406 washing Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-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 22
- 239000002904 solvent Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 239000004005 microsphere Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 14
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 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 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 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
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000001704 evaporation Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 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 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 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 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction 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
- 239000006260 foam Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000000227 grinding Methods 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
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst 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
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000005431 greenhouse gas Substances 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
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement 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, 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
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Abstract
The invention relates to the technical field of super capacitors, and discloses a nitrogen-doped porous carbon-loaded pompon NiO composite electrode material, which has more excellent conductivity and specific capacitance than pure porous carbon and nickel oxide electrode materials, wherein the porous carbon and nickel oxide in the composite material have synergistic effect, so that 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, besides, 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 the capacitance is maintained, the electrochemical property of the porous carbon material can be improved by the nitrogen-doped porous carbon, and the specific capacitance and the conductivity of the composite electrode material are further 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 grown exponentially, while the primary source of energy is the combustion of fossil fuels, but the irreversible combustion of fossil fuels generates greenhouse gases, resulting in environmental degradation, so the search for an eco-friendly and cost-effective energy source is an urgent requirement for humans to continue to live on this planet, solar and wind energy may be possible energy solutions in the future, but these two resources are not always available on demand, so there is an urgent need for a rapidly charged energy storage device that can store electrical energy for future use, supercapacitors, due to their high power density, long-term cycling stability, high safety and environmental friendliness, are considered advanced hybrid energy storage systems, but in addition to this, the specific capacitance is a major problem of supercapacitors, which is very low compared to rechargeable batteries, and most considerable research work has focused on increasing the specific capacitance of supercapacitors through electrical structuring strategies 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 pseudo capacitor, which can provide 3-4 times high capacitance using a rapid reversible surface or near-surface redox reaction, as compared with an electric double layer capacitor storing energy only by ion adsorption/desorption of the surface of an electrode material, are typical pseudo-capacitance electrode materials, in which a transition metal oxide, such as manganese oxide, cobalt oxide, nickel oxide and iron oxide, is a typical pseudo-capacitance electrode material, and in which a low cost and a theoretical higher specific capacitance are caused by various oxidation states of NiO, but NiO is an electrode material, which is inferior in conductivity, is susceptible to a volume expansion effect during charge and discharge, is inferior in stability, and a porous carbon material has the advantages of low cost and strong conductivity as a typical electrode, and a pore structure and a large specific surface area are more effective to provide more contact sites for an electrolyte, but a porous carbon is low in specific capacitance, and a theoretical capacity of the capacitor is inferior as an electrode material alone.
(one) solving the technical problems
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 poor specific capacitance of the porous carbon electrode material.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material comprises the following steps of:
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethyl methylReacting in amide to obtain 1- (4-vinyl benzyl) pyrrolidine with a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent, adding tetramethyl ethylenediamine and n-butyl lithium into the hexane solvent for polymerization reaction, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrolyl polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, then adding aluminum chloride for crosslinking reaction, filtering and washing by using ethanol after the reaction is finished, and obtaining pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide in a tube furnace, carbonizing under nitrogen atmosphere, respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) And dissolving nickel nitrate, urea and porous carbon in deionized water, uniformly stirring, transferring to a reaction kettle for hydrothermal reaction, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
Preferably, in the step (2), the mass ratio of styrene, 1- (4-vinylbenzyl) pyrrolidine, tetramethyl ethylenediamine and n-butyllithium is 100:15-40:30-40:18-22.
Preferably, the reaction temperature of the polymerization reaction in the step (2) is 50-80 ℃ and the reaction time is 2-3h.
Preferably, in the step (3), the mass ratio of the pyrrolyl polystyrene, the carbon tetrachloride, the nano silicon dioxide and the aluminum chloride is 100:800-1200:180-250:60-80.
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 between the nickel nitrate, the urea and the nitrogen doped porous carbon is 25-40:15-25:100.
Preferably, the reaction temperature of the hydrothermal reaction in the step (5) is 100-125 ℃, and the reaction time is 5-10h.
(III) beneficial 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, tetramethyl ethylenediamine is used as a regulator, n-butyllithium is used as an initiator, 1- (4-vinylbenzyl) pyrrolidine and styrene are subjected to polymerization reaction in a hexane solvent to obtain pyrrolyl polystyrene, then nano silicon dioxide is used as a pore-forming 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 firstly undergo a cross-linking reaction to obtain pyrrolyl polystyrene cross-linked microspheres coated nano silicon dioxide, then the pyrrolyl polystyrene cross-linked microspheres coated nano silicon dioxide are subjected to carbonization treatment, hydrofluoric acid is used for removing the nano silicon dioxide to obtain nitrogen-doped porous carbon, 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 precipitating agent to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
Compared with pure porous carbon and nickel oxide electrode materials, the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material has better conductivity and specific capacitance, and the porous carbon and nickel oxide in the composite material have synergistic effect, so that 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 electrochemical test, OH (OH) is formed - Fast oxidation-reduction reaction occurs in the composite electrode material and electrolyte solution, and the porous structure of the porous carbon material is OH - Provides a fast transmission channel, improves the diffusion efficiency of ions in electrolyte solution, improves the use efficiency of nickel oxide, and besidesIn 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 nickel oxide grows in situ in the porous carbon material, the porous carbon is nickel oxide, not only passes 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 with electrolyte is increased, more active sites are exposed, the electrochemical efficiency of the nickel oxide is improved, the expansion effect of the nickel oxide electrode in the using process is limited by a porous structure, the problem that the capacitance of the electrode is unstable due to powdering of the electrode material is avoided, the larger specific surface area of the electrode material is endowed by the porous structure and the pompon structure, the contact between electrolyte and the electrolyte is more sufficient, the transmission distance of ions in the electrolyte is further shortened, the using 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 diffusion resistance of the ions can be further increased, the ionic diffusion resistance of the composite electrode can be increased, the capacitance of the composite electrode can be further increased, the capacitance between the composite electrode and the capacitance can be increased, and the capacitance of the capacitance can be increased, and the capacitance between the composite electrode can be further capacitance is increased, and the capacitance is increased.
Drawings
FIG. 1 is a reaction scheme of 1- (4-vinylbenzyl) pyrrolidine with styrene.
Detailed Description
In order to achieve the above object, the present invention provides the following specific embodiments and examples: 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-vinyl benzyl) pyrrolidine with a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinylbenzyl) pyrrolidine in a hexane solvent according to the mass ratio of 100:15-40:30-40:18-22, adding tetramethyl ethylenediamine and n-butyllithium, performing polymerization reaction at 50-80 ℃ for 2-3 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:800-1200:180-250:60-80, the reaction temperature is 75-90 ℃, the reaction time is 18-36 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 580-650 ℃ for 2-4h under nitrogen atmosphere, respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) According to the ratio of 25-40:15-25:100, nickel nitrate, urea and porous carbon are dissolved in deionized water, the mixture is stirred uniformly and then transferred into a reaction kettle to carry out hydrothermal reaction at the temperature of 100-125 ℃, the reaction time is 5-10h, and after the reaction is finished, the mixture is filtered, washed and dried to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
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 a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to the mass ratio of 100:15:30:18, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 50 ℃ for 2 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:800:180:60, the reaction temperature is 75 ℃, the reaction time is 18 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 580 ℃ for 2 hours under nitrogen atmosphere, respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 25:15:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 100 ℃ for 5 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
Example 2
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100:20:32:19, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 60 ℃ for 2.2 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:900:200:65, the reaction temperature is 80 ℃, the reaction time is 24 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 600 ℃ for 2.5 hours under nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 30:18:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 110 ℃ for 6 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
Example 3
(1) Dissolving pyrrolidine, chloromethyl vinyl benzene and sodium hydride in N, N-dimethylformamide for reaction to obtain 1- (4-vinyl benzyl) pyrrolidine with a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to the mass ratio of 100:22:34:19, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 65 ℃ for 2.4 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:1000:200:70, the reaction temperature is 82 ℃, the reaction time is 28 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 610 ℃ for 3 hours under nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 32:20:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 115 ℃ for 7 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
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 a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100:30:36:20, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 70 ℃ for 2.6 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:1100:220:75, the reaction temperature is 85 ℃, the reaction time is 30 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 620 ℃ for 3 hours under nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 35:22:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 120 ℃ for 8 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
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 a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100:40:40:22, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 80 ℃ for 3 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:1200:250:80, the reaction temperature is 90 ℃, the reaction time is 36 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 650 ℃ for 4 hours under nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 40:25:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 125 ℃ for 10 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
Comparative 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 a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent according to a mass ratio of 100:10:20:12, adding tetramethyl ethylenediamine and n-butyl lithium, performing polymerization reaction at 35 ℃ for 1.4 hours, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrole-based polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, and then adding aluminum chloride for crosslinking reaction, wherein the mass ratio of the pyrrolyl polystyrene to the carbon tetrachloride to the nano silicon dioxide to the aluminum chloride is 100:600:120:40, the reaction temperature is 60 ℃, the reaction time is 12 hours, and after the reaction is finished, filtering and washing by using ethanol to obtain the pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide into a tube furnace, carbonizing at 480 ℃ for 1.4h under nitrogen atmosphere, washing with hydrofluoric acid solution and deionized water respectively, and drying to obtain nitrogen-doped porous carbon;
(5) And (3) dissolving nickel nitrate, urea and porous carbon in deionized water according to a ratio of 18:10:100, uniformly stirring, transferring to a reaction kettle, performing hydrothermal reaction at 70 ℃ for 3.5 hours, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
The method comprises the steps of carrying out electrochemical test on a composite electrode material by using a three-electrode system, wherein an electrochemical workstation is RST series, mixing and grinding the composite electrode material, acetylene black and polytetrafluoroethylene according to a mass ratio of 8.5:1.0:0.5, smearing the mixture on foam nickel, pressing the foam nickel into a working electrode under 10MPa, then taking a saturated calomel electrode as a reference electrode, taking a Pt sheet as an auxiliary electrode, and taking a 6.0M potassium hydroxide solution as an electrolyte.
Claims (8)
1. A nitrogen-doped porous carbon-loaded pompon NiO composite electrode material is 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-vinyl benzyl) pyrrolidine with a molecular formula of C 13 H 17 N；
(2) Dissolving styrene and 1- (4-vinyl benzyl) pyrrolidine in a hexane solvent, adding tetramethyl ethylenediamine and n-butyl lithium into the hexane solvent for polymerization reaction, adding ethanol into the solution after the reaction is finished, and evaporating the solvent to obtain pyrrolyl polystyrene;
(3) Fully dissolving pyrrolyl polystyrene in carbon tetrachloride, then adding nano silicon dioxide, uniformly dispersing by ultrasonic, then adding aluminum chloride for crosslinking reaction, and obtaining pyrrolyl polystyrene crosslinking microsphere coated nano silicon dioxide after the reaction is finished;
(4) Placing pyrrole-based polystyrene crosslinking microsphere coated nano silicon dioxide in a tube furnace, carbonizing under nitrogen atmosphere, respectively washing with hydrofluoric acid solution and deionized water, and drying to obtain nitrogen-doped porous carbon;
(5) And dissolving nickel nitrate, urea and porous carbon in deionized water, uniformly stirring, transferring to a reaction kettle for hydrothermal reaction, filtering, washing and drying after the reaction is finished to obtain the nitrogen-doped porous carbon-loaded pompon NiO composite electrode material.
2. The nitrogen-doped porous carbon-loaded pompon NiO composite electrode material of claim 1, wherein: in the step (2), the mass ratio of styrene, 1- (4-vinylbenzyl) pyrrolidine, tetramethyl ethylenediamine and n-butyllithium is 100:15-40:30-40:18-22.
3. The nitrogen-doped porous carbon-loaded pompon NiO composite electrode material of claim 1, wherein: 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-loaded pompon NiO composite electrode material of claim 1, wherein: in the step (3), the mass ratio of the pyrrolyl polystyrene, carbon tetrachloride, nano silicon dioxide and aluminum chloride is 100:800-1200:180-250:60-80.
5. The nitrogen-doped porous carbon-loaded pompon NiO composite electrode material of claim 1, wherein: 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-loaded pompon NiO composite electrode material of claim 1, wherein: the carbonization temperature in the step (4) is 580-650 ℃, and the carbonization time is 2-4h.
7. The nitrogen-doped porous carbon-loaded pompon NiO composite electrode material of claim 1, wherein: in the step (5), the mass ratio of nickel nitrate, urea and nitrogen doped porous carbon is 25-40:15-25:100.
8. The nitrogen-doped porous carbon-loaded pompon NiO composite electrode material of claim 1, wherein: 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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