CN112374544A - Super capacitor electrode material and preparation method thereof - Google Patents
Super capacitor electrode material and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses a super capacitor electrode material and a preparation method thereof. Preparing echinoid nano alpha-MnO by using potassium permanganate as reducing agent and manganese sulfate as manganese source and adopting hydrothermal method2Then hydroxylation modification is carried out, and click chemistry is adopted to carry out the treatment on the echinoid nano alpha-MnO2Grafting polyimide resin to obtain sea urchin-shaped nano alpha-MnO2Grafted polyimide resin, made of potassium hydroxide as the material for sea urchin-like nano alpha-MnO2The grafted polyimide resin is activated at high temperature to obtain echinoid nano alpha-MnO2And modifying the supercapacitor electrode material of the porous carbon in situ. The electrode material improves MnO2The defects of crystal lattices enhance the conductivity and stability of electrons, protons and electrons can flow freely among the crystal lattices, the rapid transfer of ions and electrons of an interface is guaranteed, a charge transfer path can be shortened, more active sites are provided for charge storage, the trapping and transfer capacity of the electrons is enhanced by the conductive material, and the mechanical stability is improved.
Description
Technical Field
The invention relates to the field of composite electrode materials of a super capacitor, in particular to a super capacitor electrode material and a preparation method thereof.
Background
Energy and environment are the foundation for human beings to live, develop and develop, and the increasingly prominent energy and environment crisis is widely noticed all over the world at present, and becomes a key factor for guiding energy and science and technology in various countries. In order to realize sustainable development of the economic society, research on renewable and green energy storage devices is carried out to become a hot spot of current scientific research.
The super capacitor is an energy storage device between a battery and a traditional electrostatic capacitor, has excellent performances of high power density, no pollution, ultra-long cycle life and the like, and is widely applied. The existing electrode materials of the super capacitor comprise carbon materials, transition metal materials and the like. Wherein MnO is2The material has the characteristics of higher theoretical capacity, no pollution, low cost, no toxicity and the like, and is considered to be a super capacitor electrode material with a great application prospect. However, a single MnO2The defects of low specific surface area, serious agglomeration, low conductivity and the like limit the application of the composite material in the field of supercapacitors. In order to improve the specific capacitance of the electrode material, composite materials are often prepared for improving the electrochemical performance of the super electrode material.
Disclosure of Invention
Based on the research background and thought, the complete technical scheme of the invention is formed as follows:
a preparation method of a supercapacitor electrode material comprises the following steps:
90 to 105 weight parts of deionized water is added with 1.9 to 2.2 weight parts of potassium permanganate and 3.0 to 3.5 weight parts of manganese sulfate, the mixture is evenly stirred, heated to 160 ℃ for reaction for 3 to 6 hours, centrifugally separated, washed and dried to prepare the sea urchin-shaped nano alpha-MnO2。
Preferably, the preparation method of the supercapacitor electrode material comprises the following steps:
(1)90 to 105 weight parts of deionized water is added with 1.9 to 2.2 weight parts of potassium permanganate and 3.0 to 3.5 weight parts of manganese sulfate, the mixture is evenly stirred, heated to 160 ℃ for reaction for 3 to 6 hours, centrifugally separated, washed and dried to prepare the sea urchin-shaped nano alpha-MnO2；
(2)500 portions of deionized water solvent and 1000 portions of echinoid nano alpha-MnO2Heating to 80-100 ℃, and reacting for 0.5-1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
(3) Under the atmosphere of nitrogen, adding 50-100 parts by weight of hydroxyl functional sea urchin-shaped nano alpha-MnO into 7.5-15 parts by weight of N, N-dimethylformamide23.75-7.5 weight parts of 2-azidoethylammonium, heating to 40-60 ℃, reacting for 20-24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
(4) Under the atmosphere of nitrogen, 10 to 20 weight portions of toluene solvent are added with 0.2 to 0.4 weight portion of acetylene end-capped polyimide resin and 3.75 to 7.5 weight portions of azide functionalized echinoid nano alpha-MnO20.0125-0.025 weight parts of blue vitriol and 0.009-0.018 weight parts of sodium ascorbate, reacting for 20-24h, centrifugally separating, washing and drying to obtain the sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) 0.05 to 0.1 weight portion of echinoid nano alpha-MnO2The grafted polyimide resin and 0.9 to 1.8 weight parts of potassium hydroxide are placed at the temperature of 800-900 ℃ for activation for 1 to 2 hours, then diluted hydrochloric acid and deionized water are respectively used for cleaning a sample until filtrate is neutral, and drying is carried out.
Preferably, the preparation method of the supercapacitor electrode material comprises the following steps:
(1)90 to 105 weight parts of deionized water is added with 1.9 to 2.2 weight parts of potassium permanganate, 3.0 to 3.5 weight parts of manganese sulfate, 1.5 to 1.8 weight parts of aluminum sulfate and 2.5 to 3.0 weight parts of cobalt sulfate, the mixture is evenly stirred, heated to 160 ℃ for reaction for 3 to 6 hours, centrifugally separated, washed and dried to prepare the sea urchin-shaped nano alpha-MnO2；
(2)500 portions of deionized water solvent and 1000 portions of echinoid nano alpha-MnO2Heating to 80-100 ℃, and reacting for 0.5-1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
(3) Under the atmosphere of nitrogen, adding 50-100 parts by weight of hydroxyl functional sea urchin-shaped nano alpha-MnO into 7.5-15 parts by weight of N, N-dimethylformamide2、3.75-7.5 parts by weight of 2-azidoethylammonium, heating to 40-60 ℃, reacting for 20-24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
(4) Under the atmosphere of nitrogen, 10 to 20 weight portions of toluene solvent are added with 0.2 to 0.4 weight portion of acetylene end-capped polyimide resin and 3.75 to 7.5 weight portions of azide functionalized echinoid nano alpha-MnO20.0125-0.025 weight parts of blue vitriol and 0.009-0.018 weight parts of sodium ascorbate, reacting for 20-24h, centrifugally separating, washing and drying to obtain the sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) 0.05 to 0.1 weight portion of echinoid nano alpha-MnO2The grafted polyimide resin and 0.9 to 1.8 weight portions of potassium hydroxide are placed at 800-2And modifying the supercapacitor electrode material of the porous carbon in situ.
The invention uses potassium permanganate as a reducing agent, manganese sulfate as a manganese source, aluminum sulfate and cobalt sulfate as Al/Co ion sources, and prepares sea urchin-shaped nano alpha-MnO by adopting a hydrothermal method2Can increase the alpha-MnO2The conductive properties of (1) can be attributed to the fact that the doping of the metal elements of Al and Co can effectively affect MnO2Structural change, increased lattice defect, reduced MnO2Internal resistance, improved conductivity, changed surface morphology, enhanced electron conductivity and stability, free flow of protons and electrons between crystal lattices, and rapid transfer of ions and electrons at interface, thereby promoting MnO2Electrochemically exhibited behavior.
The inventor further discovers that the invention is realized by aiming at echinoid nano alpha-MnO2Further research and improvement on echinoid nano alpha-MnO2Performing azide treatment, and performing click chemistry on echinoid nano alpha-MnO2Grafting polyimide resin, and finally adopting potassium hydroxide as an activating agent to carry out sea urchin-shaped nano alpha-MnO2The grafted polyimide resin is activated at high temperature to obtain echinoid nano alpha-MnO2In situ modification of polyThe electrode material of the supercapacitor with the porous carbon can effectively improve the sea urchin-shaped nano alpha-MnO2The specific surface area and easy agglomeration, and further improves the conductivity. The possible reasons for this are: sea urchin-shaped nano alpha-MnO2Forming a heterojunction with porous carbon in the sea urchin-like nano alpha-MnO2The supercapacitor electrode material with the porous carbon modified in situ can shorten a charge transfer path, provide more active sites for charge storage, enhance the trapping and transfer capacity of electrons by using the conductive material, and improve the mechanical stability. Further forming the above scheme.
The invention also discloses a super capacitor electrode material prepared by the method.
The invention also discloses a super capacitor, which comprises the super capacitor electrode.
The invention has the beneficial effects that:
the sea urchin-shaped nano alpha-MnO of the invention2The method has the advantages of cheap and easily-obtained raw materials, short reaction time, low cost, simplicity, feasibility, excellent performance, no template, no surfactant and the like. The invention uses potassium permanganate as a reducing agent, manganese sulfate as a manganese source, aluminum sulfate and cobalt sulfate as Al/Co ion sources, and prepares sea urchin-shaped nano alpha-MnO by adopting a hydrothermal method2Then to sea urchin-like nano alpha-MnO2Carrying out hydroxylation modification, and then adopting a click chemistry mode to carry out the reaction on the echinoid nano alpha-MnO2Grafting polyimide resin to obtain sea urchin-shaped nano alpha-MnO2Grafting polyimide resin, and finally adopting potassium hydroxide as activating agent to make sea urchin-shaped nano alpha-MnO2The grafted polyimide resin is activated at high temperature to obtain echinoid nano alpha-MnO2And modifying the supercapacitor electrode material of the porous carbon in situ. The invention further introduces click chemistry on the basis, and the click chemistry type reaction has the characteristics of high chemical selectivity, high yield, high reaction speed, easy formation of strong chemical bonds, high selectivity, high reaction rate, relatively mild reaction conditions and the like, and is widely applied to various fields. The invention adopts click chemistryThe method grafts MnO on polyimide resin in an 'azide-alkyne' mode2The polymer containing alkynyl can form an olefin network by self-crosslinking or generate cyclotrimerization reaction to generate a ring at high temperature, and forms a graphitized precursor in a carbon layer at high temperature by aromatization to form carbon, so that the carbon forming rate of the material can be greatly improved. Simultaneously, potassium hydroxide is adopted as an activator for echinoid nano alpha-MnO2The grafted polyimide resin is subjected to high-temperature activation treatment, so that the pore structure is easy to control and the impurity content in the porous carbon is low.
The sea urchin-shaped nano alpha-MnO of the invention2The grafted polyimide resin is carbonized at high temperature and is post-treated to obtain echinoid nano alpha-MnO with excellent performance2The possible reasons for modifying the supercapacitor electrode material of the porous carbon in situ are as follows:
on one hand, the porous network structure is beneficial to the rapid transmission of electrolyte ions in the whole electrode; secondly, the invention takes aluminum sulfate and cobalt sulfate as the ion sources of Al/Co and adopts a hydrothermal method to prepare echinoid nano alpha-MnO2The doping of Al and Co metal elements can effectively influence MnO2Structural change, increased lattice defect, reduced MnO2Internal resistance, improved conductivity, changed surface morphology, enhanced electron conductivity and stability, free flow of protons and electrons between crystal lattices, and rapid transfer of ions and electrons at interface, thereby promoting MnO2Electrochemically exhibited behavior.
On the other hand: sea urchin-shaped nano alpha-MnO2Forming a heterojunction with porous carbon in the sea urchin-like nano alpha-MnO2The supercapacitor electrode material with the porous carbon modified in situ can shorten a charge transfer path, provide more active sites for charge storage, enhance the trapping and transfer capacity of electrons by using the conductive material, and improve the mechanical stability.
Detailed Description
Parameters, sources, of specific chemicals are used.
The acetylene-terminated polyimide resin in the examples can be prepared by referring to a 2.4 synthesis method of "research on acetylene-terminated polyimide resin and carbon fiber reinforced composite material thereof" (the thesis of doctor, university of jelin, duv., 2009). Specifically, the acetylene-terminated polyimide resin is a compound with the following structural formula, wherein: n is 4, and R is methylene.
2-azidoethylamine, CAS No.: 87156-40-9.
N, N-dimethylformamide, CAS No.: 68-12-2.
Example 1
A preparation method of a supercapacitor electrode material comprises the following steps: (1) adding potassium permanganate and manganese sulfate into deionized water, stirring uniformly, heating to 160 ℃, reacting for 3h, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2；
The mass ratio of the deionized water to the potassium permanganate to the manganese sulfate is 100:2.1: 3.4;
(2) the sea urchin-shaped nano alpha-MnO2Adding into deionized water, heating to 100 deg.C, reacting for 1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
The deionized water and the echinoid nano alpha-MnO2The mass ratio of (A) to (B) is 1000: 7.5;
(3) under the nitrogen atmosphere, N, N-dimethylformamide and the hydroxyl functionalized echinoid nano alpha-MnO2Mixing with 2-azidoethylammonium, heating to 60 ℃, reacting for 24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
The N, N-dimethylformamide and hydroxyl functionalized echinoid nano alpha-MnO2The mass ratio of 2-to azidoethylammonium is 15:100: 7.5;
(4) under the atmosphere of nitrogen, 20 parts by weight of toluene solvent is added with 0.4 part by weight of acetylene-terminated polyimide resin and 7.5 parts by weight of azide functionalized echinoid nano alpha-MnO20.025 weight portions of blue vitriol and 0.018 weight portions of sodium ascorbate, react for 24 hours at 80 ℃, and are separated by centrifugation,Washing and drying to prepare sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) the sea urchin-shaped nano alpha-MnO2The grafted polyimide resin and potassium hydroxide are placed at 800 ℃ for activation for 2 hours, then diluted hydrochloric acid with 10 wt% and deionized water are respectively used for cleaning until the filtrate is neutral, and drying is carried out to prepare the sea urchin-shaped nano alpha-MnO2Modifying a supercapacitor electrode material of porous carbon in situ;
the weight of the potassium hydroxide is the echinoid nano alpha-MnO21.8 times the weight of the grafted polyimide resin.
Example 2
A preparation method of a supercapacitor electrode material comprises the following steps:
(1) adding potassium permanganate, manganese sulfate and aluminum sulfate into deionized water, stirring uniformly, heating to 160 ℃, reacting for 3 hours, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2；
The mass ratio of the deionized water to the potassium permanganate to the manganese sulfate to the aluminum sulfate is 100:2.1:3.4: 4.5;
(2) the sea urchin-shaped nano alpha-MnO2Adding into deionized water, heating to 100 deg.C, reacting for 1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
The deionized water and the echinoid nano alpha-MnO2The mass ratio of (A) to (B) is 1000: 7.5;
(3) under the nitrogen atmosphere, N, N-dimethylformamide and the hydroxyl functionalized echinoid nano alpha-MnO2Mixing with 2-azidoethylammonium, heating to 60 ℃, reacting for 24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
The N, N-dimethylformamide and hydroxyl functionalized echinoid nano alpha-MnO2The mass ratio of 2-to azidoethylammonium is 15:100: 7.5;
(4) under the atmosphere of nitrogen, 20 parts by weight of toluene solvent is added with 0.4 part by weight of acetylene-terminated polyimide resin and 7.5 parts by weight of azide functionalized echinoid nano alpha-MnO20.025 parts by weightCopper sulfate pentahydrate and 0.018 weight part of sodium ascorbate react for 24 hours at 80 ℃, and the sea urchin-shaped nano alpha-MnO is prepared by centrifugal separation, washing and drying2Grafting a polyimide resin;
(5) the sea urchin-shaped nano alpha-MnO2The grafted polyimide resin and potassium hydroxide are placed at 800 ℃ for activation for 2 hours, then diluted hydrochloric acid with 10 wt% and deionized water are respectively used for cleaning until the filtrate is neutral, and drying is carried out to prepare the sea urchin-shaped nano alpha-MnO2Modifying a supercapacitor electrode material of porous carbon in situ;
the weight of the potassium hydroxide is the echinoid nano alpha-MnO21.8 times the weight of the grafted polyimide resin.
Example 3
A preparation method of a supercapacitor electrode material comprises the following steps:
(1) adding potassium permanganate, manganese sulfate and cobalt sulfate into deionized water, stirring uniformly, heating to 160 ℃, reacting for 3 hours, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2；
The mass ratio of the deionized water to the potassium permanganate to the manganese sulfate to the cobalt sulfate is 100:2.1:3.4: 4.5;
(2) the sea urchin-shaped nano alpha-MnO2Adding into deionized water, heating to 100 deg.C, reacting for 1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
The deionized water and the echinoid nano alpha-MnO2The mass ratio of (A) to (B) is 1000: 7.5;
(3) under the nitrogen atmosphere, N, N-dimethylformamide and the hydroxyl functionalized echinoid nano alpha-MnO2Mixing with 2-azidoethylammonium, heating to 60 ℃, reacting for 24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
The N, N-dimethylformamide and hydroxyl functionalized echinoid nano alpha-MnO2The mass ratio of 2-to azidoethylammonium is 15:100: 7.5;
(4) under nitrogen atmosphere, 20 parts by weight of toluene solvent was added with 0.4 part by weight of acetylene-terminated polyimide resin,7.5 parts by weight of azide functionalized echinoid nano alpha-MnO20.025 weight parts of blue vitriol and 0.018 weight parts of sodium ascorbate, reacting for 24 hours at 80 ℃, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) the sea urchin-shaped nano alpha-MnO2The grafted polyimide resin and potassium hydroxide are placed at 800 ℃ for activation for 2 hours, then diluted hydrochloric acid with 10 wt% and deionized water are respectively used for cleaning until the filtrate is neutral, and drying is carried out to prepare the sea urchin-shaped nano alpha-MnO2Modifying a supercapacitor electrode material of porous carbon in situ;
the weight of the potassium hydroxide is the echinoid nano alpha-MnO21.8 times the weight of the grafted polyimide resin.
Example 4
A preparation method of a supercapacitor electrode material comprises the following steps:
(1) adding potassium permanganate, manganese sulfate, aluminum sulfate and cobalt sulfate into deionized water, stirring uniformly, heating to 160 ℃, reacting for 3 hours, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2；
The mass ratio of the deionized water to the potassium permanganate to the manganese sulfate to the aluminum sulfate to the cobalt sulfate is 100:2.1:3.4:1.7: 2.8;
(2) the sea urchin-shaped nano alpha-MnO2Adding into deionized water, heating to 100 deg.C, reacting for 1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
The deionized water and the echinoid nano alpha-MnO2The mass ratio of (A) to (B) is 1000: 7.5;
(3) under the nitrogen atmosphere, N, N-dimethylformamide and the hydroxyl functionalized echinoid nano alpha-MnO2Mixing with 2-azidoethylammonium, heating to 60 ℃, reacting for 24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
The N, N-dimethylformamide and hydroxyl functionalized echinoid nano alpha-MnO2The mass ratio of 2-to azidoethylammonium is 15:100: 7.5;
(4) under the atmosphere of nitrogen, 20 parts by weight of toluene solvent is added with 0.4 part by weight of acetylene-terminated polyimide resin and 7.5 parts by weight of azide functionalized echinoid nano alpha-MnO20.025 weight parts of blue vitriol and 0.018 weight parts of sodium ascorbate, reacting for 24 hours at 80 ℃, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) the sea urchin-shaped nano alpha-MnO2The grafted polyimide resin and potassium hydroxide are placed at 800 ℃ for activation for 2 hours, then diluted hydrochloric acid with 10 wt% and deionized water are respectively used for cleaning until the filtrate is neutral, and drying is carried out to prepare the sea urchin-shaped nano alpha-MnO2Modifying a supercapacitor electrode material of porous carbon in situ;
the weight of the potassium hydroxide is the echinoid nano alpha-MnO21.8 times the weight of the grafted polyimide resin.
Comparative example 1
A preparation method of a supercapacitor electrode material comprises the following steps:
adding potassium permanganate and manganese sulfate into deionized water, uniformly stirring, heating to 160 ℃, reacting for 3 hours, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO 2;
the mass ratio of the deionized water to the potassium permanganate to the manganese sulfate is 100:2.1: 3.4.
Comparative example 2
A preparation method of a supercapacitor electrode material comprises the following steps:
(1) adding potassium permanganate, manganese sulfate, aluminum sulfate and cobalt sulfate into deionized water, stirring uniformly, heating to 160 ℃, reacting for 3 hours, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2；
The mass ratio of the deionized water to the potassium permanganate to the manganese sulfate to the aluminum sulfate to the cobalt sulfate is 100:2.1:3.4:1.7: 2.8;
(2) the sea urchin-shaped nano alpha-MnO2Adding into deionized water, heating to 100 deg.C, reacting for 1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
The deionized water and the echinoid nano alpha-MnO2The mass ratio of (A) to (B) is 1000: 7.5;
(3) under the nitrogen atmosphere, N, N-dimethylformamide and the hydroxyl functionalized echinoid nano alpha-MnO2Mixing with 2-azidoethylammonium, heating to 60 ℃, reacting for 24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
The N, N-dimethylformamide and hydroxyl functionalized echinoid nano alpha-MnO2The mass ratio of 2-to azidoethylammonium is 15:100: 7.5;
(4) under the atmosphere of nitrogen, 20 parts by weight of toluene solvent is added with 0.4 part by weight of acetylene-terminated polyimide resin and 7.5 parts by weight of azide functionalized echinoid nano alpha-MnO20.025 weight parts of blue vitriol and 0.018 weight parts of sodium ascorbate, reacting for 24 hours at 80 ℃, centrifugally separating, washing and drying to prepare sea urchin-shaped nano alpha-MnO2And (3) grafting a polyimide resin.
Test example
Reference to "hierarchical porous bamboo-based carbon/MnO2Test method of composite material research (Fuxingping, Chenpezhen, proceedings of Wuyi institute of academic, 2016). Electrochemical performance tests were performed for examples 1-4 and comparative examples 1-2.
The electrochemical performance test of the electrode material is carried out by using RST5200D type electrochemical workstation, the electrode material of the super capacitor of examples 1-4 and comparative examples 1-2 is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a pure graphite sheet electrode is used as a counter electrode, 2mol/L KOH is used as electrolyte to form a three-electrode system, and the electrochemical performance test of capacitance, cycle life and the like is carried out on the electrode material under different current densities.
Preparation of a working electrode: 0.08g of the electrode material of the supercapacitor of examples 1 to 4 or comparative examples 1 to 2, 0.01g of acetylene black and 0.01g of polyvinylidene fluoride are uniformly mixed, 3 drops of N-methylpyrrolidone are added, the mixture is blended into paste and is uniformly coated on a stainless steel net with the area of 1cm multiplied by 1cm, and the paste is dried in vacuum at the temperature of 60 ℃ for 24 hours to prepare the working electrode.
TABLE 1 sea urchin-like nano alpha-MnO2In-situ repairAnd (3) comparing the capacitance of the supercapacitor electrode material decorated with porous carbon under different current densities. TABLE 2 sea urchin-like nano alpha-MnO2And the cycling efficiency table is measured under the current density of 1A/g by the supercapacitor electrode material of the in-situ modified porous carbon.
Table 1: specific capacitance (F/g) comparison table of electrode material of super capacitor under different current densities
| 1A/g | 20A/g | |
| Example 1 | 254 | 121 |
| Example 2 | 268 | 143 |
| Example 3 | 263 | 129 |
| Example 4 | 392 | 181 |
| Comparative example 1 | 110 | 71 |
| Comparative example 2 | 226 | 114 |
Compared to the alpha-MnO in comparative example 12The sea urchin-shaped nano alpha-MnO is adopted2The specific capacitance of the electrode material of the super capacitor prepared by in-situ modified porous carbon is 392F/g and 161F/g respectively under the current density of 1A/g and 20A/g, and the electrode material is compared with the pure alpha-MnO of comparative example 12Compared with the electrode material, the electrode material has great improvement and is echinoid nano alpha-MnO2The coexistence of the porous carbon and the porous carbon greatly improves the capacitance characteristic of the material, probably because the doping of Al and Co metal elements can effectively influence MnO2Structural change, increased lattice defect, reduced MnO2Internal resistance, improved conductivity, changed surface morphology, enhanced electron conductivity and stability, free flow of protons and electrons between crystal lattices, and rapid transfer of ions and electrons at interface, thereby promoting MnO2Electrochemically exhibited behavior. At the same time, sea urchin-shaped nano alpha-MnO2Forming a heterojunction with porous carbon in the sea urchin-like nano alpha-MnO2The supercapacitor electrode material with the porous carbon modified in situ can shorten a charge transfer path, provide more active sites for charge storage, enhance the trapping and transfer capacity of electrons by using the conductive material, and improve the mechanical stability. Example 4 also gives a factual corroboration of the capacitive properties, in comparison with the electrochemical tests of comparative example 1.
Table 2: cycling efficiency table of supercapacitor electrode material measured at current density of 1A/g
| 10000 times (%) | |
| Example 1 | 71.6 |
| Example 2 | 80.9 |
| Example 3 | 75.2 |
| Example 4 | 90.5 |
| Comparative example 1 | 59.7 |
| Comparative example 2 | 65.1 |
Example 4 sea urchin-like Nano α -MnO2The supercapacitor electrode material prepared by in-situ modified porous carbon is subjected to constant current charge and discharge for 10000 times in 2mol/L KOH solution at a current density of 1A/g, and the specific capacitance of the material keeps 90.5% of the initial capacitance after 10000 charge and discharge cycles, which indicates that the electrode material has good stability.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (5)
1. A preparation method of a supercapacitor electrode material comprises the following steps:
90-105 weightAdding 1.9-2.2 parts by weight of potassium permanganate and 3.0-3.5 parts by weight of manganese sulfate into deionized water, uniformly stirring, heating to 140-2。
2. A preparation method of a supercapacitor electrode material comprises the following steps:
(1)90 to 105 weight parts of deionized water is added with 1.9 to 2.2 weight parts of potassium permanganate and 3.0 to 3.5 weight parts of manganese sulfate, the mixture is evenly stirred, heated to 160 ℃ for reaction for 3 to 6 hours, centrifugally separated, washed and dried to prepare the sea urchin-shaped nano alpha-MnO2；
(2)500 portions of deionized water solvent and 1000 portions of echinoid nano alpha-MnO2Heating to 80-100 ℃, and reacting for 0.5-1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
(3) Under the atmosphere of nitrogen, adding 50-100 parts by weight of hydroxyl functional sea urchin-shaped nano alpha-MnO into 7.5-15 parts by weight of N, N-dimethylformamide23.75-7.5 weight parts of 2-azidoethylammonium, heating to 40-60 ℃, reacting for 20-24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
(4) Under the atmosphere of nitrogen, 10 to 20 weight portions of toluene solvent are added with 0.2 to 0.4 weight portion of acetylene end-capped polyimide resin and 3.75 to 7.5 weight portions of azide functionalized echinoid nano alpha-MnO20.0125-0.025 weight parts of blue vitriol and 0.009-0.018 weight parts of sodium ascorbate, reacting for 20-24h, centrifugally separating, washing and drying to obtain the sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) 0.05 to 0.1 weight portion of echinoid nano alpha-MnO2The grafted polyimide resin and 0.9 to 1.8 weight parts of potassium hydroxide are placed at the temperature of 800-900 ℃ for activation for 1 to 2 hours, then diluted hydrochloric acid and deionized water are respectively used for cleaning a sample until filtrate is neutral, and drying is carried out.
3. A preparation method of a supercapacitor electrode material comprises the following steps:
(1)90 to 105 weight parts of deionized water is added with 1.9 to 2.2 weight parts of potassium permanganate, 3.0 to 3.5 weight parts of manganese sulfate, 1.5 to 1.8 weight parts of aluminum sulfate and 2.5 to 3.0 weight parts of cobalt sulfate, the mixture is evenly stirred, heated to 160 ℃ for reaction for 3 to 6 hours, centrifugally separated, washed and dried to prepare the sea urchin-shaped nano alpha-MnO2；
(2)500 portions of deionized water solvent and 1000 portions of echinoid nano alpha-MnO2Heating to 80-100 ℃, and reacting for 0.5-1h to obtain hydroxyl functionalized sea urchin-shaped nano alpha-MnO2；
(3) Under the atmosphere of nitrogen, adding 50-100 parts by weight of hydroxyl functional sea urchin-shaped nano alpha-MnO into 7.5-15 parts by weight of N, N-dimethylformamide23.75-7.5 weight parts of 2-azidoethylammonium, heating to 40-60 ℃, reacting for 20-24h, centrifugally separating, washing and drying to prepare azido functionalized echinoid nano alpha-MnO2；
(4) Under the atmosphere of nitrogen, 10 to 20 weight portions of toluene solvent are added with 0.2 to 0.4 weight portion of acetylene end-capped polyimide resin and 3.75 to 7.5 weight portions of azide functionalized echinoid nano alpha-MnO20.0125-0.025 weight parts of blue vitriol and 0.009-0.018 weight parts of sodium ascorbate, reacting for 20-24h, centrifugally separating, washing and drying to obtain the sea urchin-shaped nano alpha-MnO2Grafting a polyimide resin;
(5) 0.05 to 0.1 weight portion of echinoid nano alpha-MnO2The grafted polyimide resin and 0.9 to 1.8 weight parts of potassium hydroxide are placed at the temperature of 800-900 ℃ for activation for 1 to 2 hours, then diluted hydrochloric acid and deionized water are respectively used for cleaning a sample until filtrate is neutral, and drying is carried out.
4. An electrode material for a supercapacitor, which is prepared by the method of claim 1, 2 or 3.
5. A supercapacitor comprising an electrode, wherein the material of the electrode is the supercapacitor electrode material according to claim 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114068935A (en) * | 2021-11-15 | 2022-02-18 | 大连理工大学 | High-activity Mn/Co-N double-site doped carbon material catalyst, preparation method and application thereof in lithium-sulfur battery |
| CN114300277A (en) * | 2021-12-28 | 2022-04-08 | 辽宁大学 | Aluminum manganese oxide and application thereof as anode material in water system magnesium ion capacitor |
| TWI795196B (en) * | 2022-01-26 | 2023-03-01 | 國立臺灣科技大學 | Electrode material including binary metal oxide, method for preparing electrode including the same, and supercapacitor |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114068935A (en) * | 2021-11-15 | 2022-02-18 | 大连理工大学 | High-activity Mn/Co-N double-site doped carbon material catalyst, preparation method and application thereof in lithium-sulfur battery |
| CN114068935B (en) * | 2021-11-15 | 2023-01-24 | 大连理工大学 | High-activity Mn/Co-N dual-site doped carbon material catalyst, preparation method and application thereof in lithium-sulfur battery |
| CN114300277A (en) * | 2021-12-28 | 2022-04-08 | 辽宁大学 | Aluminum manganese oxide and application thereof as anode material in water system magnesium ion capacitor |
| TWI795196B (en) * | 2022-01-26 | 2023-03-01 | 國立臺灣科技大學 | Electrode material including binary metal oxide, method for preparing electrode including the same, and supercapacitor |
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