CN114684803A - Method for preparing porous carbon composite material with nickel/cobalt microparticles loaded on surface by using high internal phase emulsion template - Google Patents
Method for preparing porous carbon composite material with nickel/cobalt microparticles loaded on surface by using high internal phase emulsion template Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 37
- 239000010941 cobalt Substances 0.000 title claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011859 microparticle Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000839 emulsion Substances 0.000 title claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 9
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 21
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 21
- 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 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007772 electrode material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 11
- 230000033228 biological regulation Effects 0.000 abstract description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010351 charge transfer process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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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 belongs to the technical field of electrochemical material preparation, and particularly relates to a method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template. The preparation method adopts a high internal phase emulsion template method, realizes the preparation of the porous carbon composite material with nickel/cobalt microparticles loaded on the surface through polymerization, simple self-crosslinking and pyrolysis, and realizes the regulation and control of the content of nickel and cobalt by changing the ratio of the quantity concentration of nickel ions and cobalt ions in the aqueous solution. The prepared porous carbon composite material has high nickel-cobalt loading capacity, and the supercapacitor prepared by taking the prepared porous carbon composite material with nickel/cobalt microparticles loaded on the surface as an electrode shows good electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of electrochemical material preparation, and particularly relates to a method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template.
Background
Supercapacitors, which are considered as novel energy storage devices between conventional capacitors and batteries, can release a large amount of electrical energy in a short time compared to conventional energy storage assemblies, and have received much attention due to their excellent power density, high charge and discharge rates, long service life and cycle stability. In general, the type and morphology of the electrode material are decisive factors for the high and low electrochemical performance of the supercapacitor. According to the energy storage mechanism of the supercapacitor, electrode materials thereof may be classified into two types, one of which stores energy by an interfacial double layer formed between the electrode material and an electrolyte, such as a carbon material; another class is the storage of electrical energy by highly reversible redox reactions that occur between the electrode material and the electrolyte, such as transition metal compounds and conducting polymers. As an important electrode material of a super capacitor, although the theoretical specific capacitance of a transition metal compound is very high, the conductivity of the transition metal compound is very low, so that the actual capacitance of the prepared electrode material is far lower than the theoretical predicted value of the prepared electrode material; the electrode has higher resistivity, so that the transfer of electrolyte ions is influenced, and the resistance of the electrode is increased; and the process of storing charges of the electrode only occurs on the surface of the transition metal compound material, and the whole material is not fully utilized. While some transition metal compounds such as RuO2Its large-scale commercial application is limited due to the shortage of natural resources. Therefore, the development of the metal compound composite material is a more ideal choice。
The porous carbon material is most widely applied due to the basic characteristics of excellent conductivity, chemical stability, large specific surface area, abundant sources, low cost and the like, and shows great application potential in the electrode material of the super capacitor. In the method for obtaining the porous carbon, the pore state of the porous carbon can be accurately regulated and controlled by a template method, so that electrolyte ions can be rapidly transferred and accumulated in a material with proper pore distribution, and the resistance is reduced.
The method for synthesizing the metal compound composite material by taking the carbon material as the substrate is widely considered as a feasible effective means for improving the electrochemical performance of the metal compound in the aspect of the super capacitor, however, the carbon material used as the substrate is usually an expensive material which is difficult to prepare such as graphene, carbon nanotubes, carbon quantum dots and the like, and the large-scale production and application of the composite material are severely limited.
The metal compound composite porous carbon is derived and synthesized by a high internal phase emulsion template method, the method is simple, the cost is low, the porous carbon is used as an electron transmission bridge, the electric activity of the metal-based nanoparticles can be obviously enhanced, and the internal clear pore channel can effectively promote the electrolyte diffusion in the electrochemical test process; furthermore, the metal-based nanoparticles are located on interconnected carbon frameworks, which can greatly enhance the charge transfer process. Therefore, the structure can keep higher integrity, improve the conductivity, shorten the reaction path when the oxidation-reduction reaction occurs, thereby providing excellent electrochemical performance, and is expected to become one of important research directions with full vitality and application prospects. The preparation method adopts a high internal phase emulsion template method, realizes the preparation of the porous carbon composite material with nickel/cobalt microparticles loaded on the surface through polymerization, simple self-crosslinking and pyrolysis, and realizes the regulation and control of the content of nickel and cobalt by changing the ratio of the quantity concentration of nickel ions and cobalt ions in the aqueous solution.
Disclosure of Invention
The invention aims to solve the problems of complicated steps and high cost in the synthesis of a metal compound composite carbon material aiming at the defects of the prior art, and provides a method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template. The content of nickel and cobalt can be regulated and controlled by changing the ratio of the quantity concentration of nickel ions to the concentration of cobalt ions in the aqueous solution.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template comprises the following specific steps:
(1) completely dissolving a certain proportion of monomers, an initiator and a surfactant in toluene to prepare an oil phase;
(2) slowly dropwise adding a sodium alginate aqueous solution with a certain concentration as a water phase into the oil phase obtained in the step (1) under the condition of mechanical stirring, continuously stirring for 90 min to obtain a uniform emulsion after dropwise adding is completed within half an hour, and then stirring at a high speed for 3-5 min to obtain a water-in-oil type high internal phase emulsion;
(3) sealing the high internal phase emulsion obtained in the step (2), and then carrying out polymerization reaction at 70 ℃ for 24 hours to obtain a solid block-shaped crude product;
(4) soaking the solid block-shaped crude product obtained in the step (3) in aqueous solution of nickel ions and cobalt ions with certain concentration, taking out the crude product after 72 hours, washing the crude product, and freeze-drying the washed product to obtain a polymer precursor;
(5) and (4) pyrolyzing the polymer precursor obtained in the step (4) at 700 ℃ under the protection of nitrogen for 1 h to obtain the porous carbon composite material with the surface loaded with nickel/cobalt microparticles.
Further, the monomer in the step (1) is divinylbenzene or a mixture of divinylbenzene and styrene.
Further, the initiator in the step (1) is azobisisobutyronitrile or dibenzoyl peroxide.
Further, the surfactant in the step (1) is span 80.
The mass fraction of the surfactant in the oil phase in the step (1) is 10%.
Further, the concentration of the sodium alginate aqueous solution in the step (2) is 1-2 wt%.
The volume of the water phase in the step (2) accounts for 85% of the total volume of the water-in-oil type high internal phase emulsion in the step (2).
Further, the aqueous solution containing a certain amount of nickel ions and cobalt ions in the step (4) is an aqueous solution of nickel nitrate and cobalt nitrate.
Further, the ratio of the amount concentration of the cobalt nitrate to the amount concentration of the nickel nitrate is 0:10 to 10: 0.
The application comprises the following steps: the porous carbon composite material with the nickel/cobalt microparticles loaded on the surface is applied to preparing a super capacitor as an electrode material.
The invention has the beneficial effects that:
(1) the invention develops a method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template. The porous carbon composite material with nickel/cobalt microparticles loaded on the surface is synthesized in one step only by once pyrolysis. The porous carbon composite materials with different contents of nickel/cobalt microparticles loaded on the surfaces are prepared by adjusting the ratio of the quantity concentration of the cobalt nitrate to the nickel nitrate.
(2) During pyrolysis, the cross-linked nickel cobalt ions are reduced to nickel/cobalt microparticles. Thanks to the interconnected pores left after the removal of the external phase and the micropores caused by the chemical activation of the nitrate, the composite material forms a hierarchical porous structure with interconnected macropores, mesopores and micropores, which provides a larger specific surface area and a large number of electrochemically active sites, thereby effectively improving the specific capacitance of the electrode material.
(3) Raman spectroscopy with increasing ratio of the quantity concentrations of cobalt nitrate and nickel nitrate speciesI D/I GThe carbon material is firstly reduced and then increased, which shows that the graphitization degree of the carbon material is firstly increased and then reduced, and the increase of the graphitization degree is beneficial to the enhancement of the conductivity of the carbon material, thereby realizing the regulation and control of the graphitization degree of the carbon material.
(4) The porous carbon composite material with the nickel/cobalt microparticles loaded on the surface is prepared by utilizing the high internal phase emulsion template, so that the nickel/cobalt microparticles are loaded on porous carbon pore channels, wherein the porous carbon is used as a bridge for electron transmission, the electrical activity of the nickel/cobalt microparticles can be obviously enhanced, and the pore channels with rich internal layers can effectively promote the electrolyte diffusion in the electrochemical test process; in addition, the nickel/cobalt microparticles are located on interconnected carbon frameworks, which can greatly enhance the charge transfer process. Therefore, the structure can maintain high integrity, improve conductivity, and shorten a reaction path when a redox reaction occurs, thereby providing excellent electrochemical performance.
Drawings
FIG. 1 is an electron microscope image of a porous carbon composite material with nickel/cobalt microparticles loaded on the surface prepared in example 3; wherein, a and b: electron micrograph before pyrolysis, c, d: electron microscopy images after pyrolysis;
fig. 2 is a nitrogen adsorption and desorption test chart of the porous carbon composite materials with nickel/cobalt microparticles loaded on the surfaces prepared in examples 1, 2, 3, 4 and 5 and comparative examples 1 and 2;
fig. 3 is a raman spectrum of the porous carbon composite materials having nickel/cobalt microparticles supported on the surface prepared in examples 1, 2, 3, 4, 5 and comparative examples 1 and 2;
FIG. 4 is an X-ray diffraction pattern of the porous carbon composite materials having nickel/cobalt microparticles supported on the surface prepared in examples 1, 2, 3, 4, 5 and comparative examples 1 and 2;
fig. 5 is a constant current charge and discharge curve diagram of the porous carbon composite materials with nickel/cobalt microparticles loaded on the surfaces prepared in examples 1, 2, 3, 4 and 5 and comparative examples 1 and 2.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
Firstly, dissolving divinylbenzene, azodiisobutyronitrile and span-80 in toluene to obtain an oil phase, wherein the adding amount of the azodiisobutyronitrile is 1.25 percent of the mass of the divinylbenzene, the mass fraction of the span-80 in the oil phase is 10 percent, and the volume ratio of the divinylbenzene to the toluene is 1: 1; slowly dripping 1.5wt% sodium alginate aqueous solution into the oil phase (dripping is completed within 30 min) under the mechanical stirring condition with the rotation speed of 550 rpm, continuing stirring for 90 min after dripping is completed, and stirring for 3 min under the high-speed stirring with the rotation speed of 15000 rpm to obtain the water-in-oil type high internal phase emulsion with the internal phase volume fraction of 85%; carrying out polymerization reaction at 70 ℃ after sealing, and obtaining a solid block-shaped crude product after reaction for 24 hours; and (3) soaking the solid massive crude product in a mixed aqueous solution of cobalt nitrate and nickel nitrate with the total concentration of 2 mol/L, taking out the mixed aqueous solution after 72 hours, washing, freezing in a low-temperature refrigerator, freeze-drying, and pyrolyzing the obtained polymer precursor at 700 ℃ for 1 hour under the protection of nitrogen to obtain the porous carbon composite material with the nickel/cobalt microparticles loaded on the surface.
Example 2: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to that of nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 3: 7.
Example 3: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 5: 5.
Example 4: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 7: 3.
Example 5: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 9: 1.
Comparative example 1: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 0: 10.
Comparative example 2: the specific experimental procedure was the same as in example 1, and the ratio of the mass concentration of cobalt nitrate to that of nickel nitrate in the prepared mixed aqueous solution of cobalt nitrate and nickel nitrate was 10: 0.
TABLE 1 data of porous carbon composites with nickel/cobalt microparticles loaded on the surface prepared under different conditions
Figure 1 illustrates that sodium alginate-nickel cobalt gel in the internal phase is loaded on a high molecular polymer before pyrolysis, and the sodium alginate-nickel cobalt gel is reduced to form nickel/cobalt microparticles after pyrolysis at high temperature. Meanwhile, the high molecular polymer still keeps a good hierarchical porous structure after pyrolysis.
Fig. 2 illustrates that the composite forms a hierarchical porous structure having macropores, mesopores, and micropores.
FIG. 3 illustrates Raman spectra for cobalt nitrate and nickel nitrate species with increasing concentration ratiosI D/I GThe nickel ions and the cobalt ions can catalyze the graphitization degree of the carbon material during pyrolysis, the catalytic effect is increased firstly and then reduced along with the increase of the ratio of the amount concentration of the cobalt to the amount concentration of the nickel, and the increase of the graphitization degree is beneficial to the enhancement of the conductivity of the carbon material.
Fig. 4 illustrates that all peaks correspond well to the (111), (200), (220) crystal planes of Co and Ni, demonstrating that porous carbon composite materials with nickel/cobalt microparticles supported on the surface are formed after pyrolysis.
FIG. 5 illustrates that as the ratio of the quantity concentration of cobalt nitrate to nickel nitrate increases, the specific capacitance of the porous carbon composite material with nickel/cobalt microparticles loaded on the surface increases and then decreases, and the highest capacitance reaches 498.5F g-1。
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A method for preparing a porous carbon composite material with nickel/cobalt microparticles loaded on the surface by using a high internal phase emulsion template is characterized by comprising the following steps:
(1) completely dissolving a monomer, an initiator and a surfactant in toluene to prepare an oil phase;
(2) slowly dropwise adding a sodium alginate aqueous solution with a certain concentration as a water phase into the oil phase obtained in the step (1) under the condition of mechanical stirring, continuously stirring for 90 min to obtain a uniform emulsion after dropwise adding is completed within half an hour, and then stirring at a high speed for 3-5 min to obtain a water-in-oil type high internal phase emulsion;
(3) sealing the high internal phase emulsion obtained in the step (2), and then carrying out polymerization reaction for 24 hours at 70 ℃ to obtain a solid block-shaped crude product;
(4) soaking the solid block-shaped crude product obtained in the step (3) in an aqueous solution containing nickel ions and cobalt ions with certain concentration, taking out after 72 hours, washing, and freeze-drying to obtain a polymer precursor;
(5) and (4) pyrolyzing the polymer precursor obtained in the step (4) at 700 ℃ under the protection of nitrogen for 1 h to obtain the porous carbon composite material with the surface loaded with nickel/cobalt microparticles.
2. The method of claim 1, wherein: the monomer in the step (1) is divinylbenzene or a mixture of divinylbenzene and styrene.
3. The method of claim 1, wherein: the initiator in the step (1) is azobisisobutyronitrile or dibenzoyl peroxide.
4. The method of claim 1, wherein: the surfactant in the step (1) is span 80, and the mass fraction of the surfactant in the oil phase is 10%.
5. The method of claim 1, wherein: the mass percentage concentration of the sodium alginate aqueous solution in the step (2) is 1-2%.
6. The method of claim 1, wherein: the aqueous solution of nickel ions and cobalt ions in the step (4) is an aqueous solution of nickel nitrate and cobalt nitrate, wherein the ratio of the quantity concentration of the cobalt nitrate to the quantity concentration of the nickel nitrate is 0: 10-10: 0.
7. Porous carbon composite material having nickel/cobalt microparticles supported on the surface thereof, produced by the method according to any one of claims 1 to 6.
8. The application of the porous carbon composite material with nickel/cobalt microparticles loaded on the surface, which is disclosed by claim 7, as an electrode material in preparation of a supercapacitor.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142080A (en) * | 2017-05-02 | 2017-09-08 | 南京航空航天大学 | A kind of adjustable CoNi/ porous carbons microwave absorption of ratio and preparation method thereof |
| US20170373305A1 (en) * | 2016-06-22 | 2017-12-28 | Sharp Kabushiki Kaisha | Porous carbon-metal/alloy composite material, synthesis method, and electrode including same |
| CN108831756A (en) * | 2018-07-02 | 2018-11-16 | 桂林电子科技大学 | It is a kind of that nickel, porous carbon composite of cobalt and its preparation method and application are adulterated based on ZIF-8 |
| CN109336083A (en) * | 2018-10-15 | 2019-02-15 | 福州大学 | A kind of method of High Internal Phase Emulsion template controllable preparation foamy carbon/carbon nano tube compound material |
| CN109346332A (en) * | 2018-10-17 | 2019-02-15 | 上海交通大学 | Lithium ion mixed capacitor and preparation method thereof based on alginic acid cross-linked structure |
| CN109650373A (en) * | 2019-01-29 | 2019-04-19 | 河北省科学院能源研究所 | A kind of copper load sodium alginate carbon aerogels and its preparation method and application |
| CN110228808A (en) * | 2019-05-30 | 2019-09-13 | 福州大学 | A kind of High Internal Phase Emulsion template of the interior phase preparing porous carbon materials-foreign minister's collaboration |
| CN112239201A (en) * | 2020-11-30 | 2021-01-19 | 福州大学 | Method for preparing nitrogen-sulfur double-doped porous carbon through one-step carbonization |
| CN113398883A (en) * | 2021-06-12 | 2021-09-17 | 清华大学深圳国际研究生院 | Preparation method and application of iron carbide/manganese crosslinked sodium alginate composite material |
-
2022
- 2022-03-31 CN CN202210331825.6A patent/CN114684803B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170373305A1 (en) * | 2016-06-22 | 2017-12-28 | Sharp Kabushiki Kaisha | Porous carbon-metal/alloy composite material, synthesis method, and electrode including same |
| CN107142080A (en) * | 2017-05-02 | 2017-09-08 | 南京航空航天大学 | A kind of adjustable CoNi/ porous carbons microwave absorption of ratio and preparation method thereof |
| CN108831756A (en) * | 2018-07-02 | 2018-11-16 | 桂林电子科技大学 | It is a kind of that nickel, porous carbon composite of cobalt and its preparation method and application are adulterated based on ZIF-8 |
| CN109336083A (en) * | 2018-10-15 | 2019-02-15 | 福州大学 | A kind of method of High Internal Phase Emulsion template controllable preparation foamy carbon/carbon nano tube compound material |
| CN109346332A (en) * | 2018-10-17 | 2019-02-15 | 上海交通大学 | Lithium ion mixed capacitor and preparation method thereof based on alginic acid cross-linked structure |
| CN109650373A (en) * | 2019-01-29 | 2019-04-19 | 河北省科学院能源研究所 | A kind of copper load sodium alginate carbon aerogels and its preparation method and application |
| CN110228808A (en) * | 2019-05-30 | 2019-09-13 | 福州大学 | A kind of High Internal Phase Emulsion template of the interior phase preparing porous carbon materials-foreign minister's collaboration |
| CN112239201A (en) * | 2020-11-30 | 2021-01-19 | 福州大学 | Method for preparing nitrogen-sulfur double-doped porous carbon through one-step carbonization |
| CN113398883A (en) * | 2021-06-12 | 2021-09-17 | 清华大学深圳国际研究生院 | Preparation method and application of iron carbide/manganese crosslinked sodium alginate composite material |
Non-Patent Citations (2)
| Title |
|---|
| 黄伟杰;: "镍钴/碳气凝胶的制备及电催化析氧性能研究", 云南化工, no. 12, pages 44 - 45 * |
| 黄敏;刘兴勇;李玉宝;张利;: "海藻酸钠微球制备工艺优化及其对球形及粒径的影响", 四川理工学院学报(自然科学版), no. 02, pages 1 - 6 * |
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