CN111029171A - Porous AB without adhesive2O4Preparation method of @ M electrode - Google Patents
Porous AB without adhesive2O4Preparation method of @ M electrode Download PDFInfo
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- CN111029171A CN111029171A CN201911342189.1A CN201911342189A CN111029171A CN 111029171 A CN111029171 A CN 111029171A CN 201911342189 A CN201911342189 A CN 201911342189A CN 111029171 A CN111029171 A CN 111029171A
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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
- H01G11/84—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- Y02E60/10—Energy storage using batteries
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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 discloses a porous AB without an adhesive2O4The preparation method of the @ M electrode mainly comprises the steps of dissolving nitrates of metals A and B in water, adding fuel, stirring to obtain reaction liquid, immersing a pretreated current collector M in the reaction liquid, placing the current collector M in a preheated heating furnace, heating until combustion reaction occurs, taking out the reacted current collector after the reaction is finished, and carrying out post-treatment to obtain the binderless porous AB electrode2O4The @ M electrode. The preparation method is simple, short in time consumption, relatively mild in reaction conditions, easy to operate, low in equipment investment and easy for large-scale production; growing porous AB directly on current collector2O4The use of conductive agents and binders is reduced, the manufacturing cost is saved, and the energy storage performance of the electrode is improved; binderless porous AB2O4Application of @ M electrode in super capacitor, lithium ion battery, electrocatalysis and other fieldsThe domain has wide application prospect.
Description
Technical Field
The invention relates to the field of energy storage material preparation and nano manufacturing, in particular to a porous AB without an adhesive2O4A preparation method of the @ M electrode.
Background
Spinel type bimetal oxide (AB)2O4) Is an important inorganic functional materialThe material has the advantages of high melting point, good thermal stability, corrosion resistance and the like, has wide application prospect in the fields of photocatalysis, electrocatalysis, electric energy storage and the like, and has attracted extensive attention of people. Spinel type bimetal oxide is used as an energy storage electrode material, and attracts people with excellent characteristics. The spinel-type bimetal oxide stores energy by redox reactions occurring on the surface of the active material and in the bulk phase, and thus has higher energy density and specific capacity, compared to conventional carbon materials. In addition, the spinel type bimetal oxide also has the advantages of controllable shape, size and size, abundant raw materials, easy material acquisition and the like. Thus, spinel-type bimetallic oxides are very promising electrode materials.
The preparation method of the powder material electrode generally comprises the steps of dispersing an electroactive substance, a conductive agent and a binder in a solvent to form a paste, then coating the paste on a current collector, and combining the subsequent procedures of drying, pressing and the like to prepare the electrode slice. In the preparation process of the electrode, a binder, a conductive agent and a solvent are required, which increases the production cost, decreases the utilization rate of active ingredients, and prolongs the preparation period of the electrode. In addition, the degree of binding of the active ingredient to the current collector also affects the cycle stability of the electrode.
At present, the preparation methods of spinel-type metal oxide binderless electrodes include hydrothermal methods, solvothermal methods, electrodeposition methods, and the like, such as: the physical chemistry newspaper, vol.36, 2020, Yongli et al, NiCo-based2O4In the article of asymmetric hybrid capacitor with nanosheet electrode, it is reported that nickel cobaltate nanosheets are grown on a foamed nickel substrate by a simple hydrothermal method, and the nickel cobaltate nanosheets are directly used as supercapacitor electrodes and show excellent electrochemical performance. In the text of "electro-catalytic oxygen evolution Performance of anodic electro-deposition Co-Ni Mixed oxides in alkaline Medium" at volume 25, 2004, Vol.25, Wugang et al, based on electrochemical anodic codeposition technique, from Co-containing materials of different Co2+/Ni2 +In the NaOH solution, Co-Ni mixed oxide was prepared on a Ni substrate. However, the traditional method for preparing the binderless electrode has the defects of long reaction time, complex synthesis steps and loadLow amount, and the like.
The solution combustion method is a simple method for preparing metal oxide, and the heat released by the reaction is utilized to maintain the reaction, so that the method has the advantages of energy conservation and high speed, and becomes one of ideal choices of low-cost preparation methods. If the spinel porous bimetal oxide can be directly grown on the surface of the conductive substrate by using a solution combustion method, the use of a binder and a conductive agent in the preparation process of the electrode can be reduced, the manufacturing process of the electrode is further simplified, the production cost is reduced, and the utilization rate of an electroactive material, the stability of the electrode and the service life of the electrode can be favorably improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a porous AB without an adhesive2O4The preparation method of the @ M electrode is simple in preparation process, simple and convenient to operate, free of complex equipment and low in cost, and is suitable for batch production.
The technical scheme of the invention is as follows: porous AB without adhesive2O4The preparation method of the @ M electrode comprises the following specific steps:
(1) dissolving nitrate of metal A, B in water, adding fuel and stirring to obtain reaction liquid;
(2) immersing a pretreated current collector M in the reaction solution;
(3) heating the reaction solution containing M in a preheated heating furnace until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted current collector, and performing post-treatment to obtain the binderless porous AB2O4The @ M electrode.
Further, the nitrates of the metal A, B used in step 1 were two selected from nickel nitrate, cobalt nitrate, copper nitrate, manganese nitrate, and zinc nitrate.
Further, the fuel used in step 1 is glycine or urea.
Further, the molar ratio of A to B in step 1 was 1: 2.
Further, the current collector M used in step 2 is a nickel foam, a copper foam or a titanium mesh.
Further, the pretreatment process of the current collector M used in the step 2 is to ultrasonically soak the current collector M for 30min by using 2 mol/L hydrochloric acid, ultrasonically clean the current collector M by using water and ethanol, and naturally dry the current collector M.
Further, the preheating temperature of the heating furnace in the step 3 is 300 ℃.
Further, the post-treatment process in the step 4 is to wash the reacted M with water and ethanol in sequence, and then dry the M at 60-90 ℃.
The invention has the beneficial effects that:
1. the preparation method of the electrode disclosed by the invention directly grows the porous spinel type bimetal oxide on the conductive agent substrate, reduces the use of the conductive agent and the binder, reduces the manufacturing steps of the electrode and reduces the manufacturing cost of the electrode;
2. the porous spinel type bimetal oxide directly grows on the conductive agent substrate, which is beneficial to improving the combination degree of the metal oxide and the conductive substrate and the utilization rate of electroactive substances, thereby further improving the capacity and stability of the electrode and having wide application prospect in the fields of super capacitors, lithium ion batteries, electrocatalysis and the like;
3. the invention discloses a porous AB without an adhesive2O4The preparation process of the @ M electrode is simple, the operation is simple and convenient, the reaction conditions are relatively mild, complex equipment is not needed, the consumed time is short, and the method is suitable for batch production.
Drawings
FIG. 1 is a binderless porous NiCo prepared in example 12O4FESEM photograph of @ Ni electrode;
FIG. 2 is a binder-free porous MnCo prepared in example 22O4FESEM photograph of @ Ni electrode;
FIG. 3 is a binder-free porous MnCo prepared in example 32O4FESEM photograph of @ Ti electrode;
FIG. 4 is the binderless porous ZnCo prepared in example 42O4FESEM photograph of @ Ni electrode;
FIG. 5 is a binderless porous NiMn as prepared in example 52O4FESEM photograph of @ Ni electrode;
FIG. 6 is a binderless porous CoMn as prepared in example 62O4FESEM photograph of @ Ni electrode;
FIG. 7 is a binderless porous ZnMn of example 72O4FESEM photograph of @ Ni electrode;
FIG. 8 is a binder-free porous MnCo prepared in example 82O4FESEM photograph of @ Cu electrode;
FIG. 9 is a binderless porous CuMn as prepared in example 92O4FESEM photograph of @ Ni electrode.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
EXAMPLE 1A Binderless porous NiCo2O4Preparation of @ Ni electrode
(1) Dissolving 0.582 g of nickel nitrate hexahydrate and 1.161 g of cobalt nitrate hexahydrate in 10.0 mL of water, adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at 60 ℃ to obtain the binderless porous NiCo2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 1. As can be seen from fig. 1, the electrode has a porous structure.
Example 2A Binderless porous MnCo2O4Preparation of @ Ni electrode
(1) Dissolving 0.358 g of hydrated manganese nitrate and 1.161 g of cobalt nitrate hexahydrate in 10.0 mL of water, then adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at 90 ℃ to obtain binderless porous MnCo2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 2. As can be seen from fig. 2, the electrode has a porous structure.
Example 3A Binderless porous MnCo2O4Preparation of @ Ti electrode
(1) Dissolving 0.358 g of hydrated manganese nitrate and 1.161 g of cobalt nitrate hexahydrate in 10.0 mL of water, then adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a titanium net in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the titanium net with water and ethanol, naturally airing the titanium net, and then soaking the pretreated titanium net in a reaction solution;
(3) heating the reaction solution containing the titanium net in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the titanium mesh after the reaction, ultrasonically washing the titanium mesh by water and ethanol, and drying the titanium mesh at 70 ℃ to obtain binderless porous MnCo2O4The @ Ti electrode, an SEM photograph of the electrode is shown in FIG. 3. As can be seen from fig. 3, the electrode is a porous structure composed of nanosheets.
Example 4A Binderless porous ZnCo2O4Preparation of @ Ni electrode
(1) Dissolving 0.601 g of zinc nitrate hexahydrate and 1.161 g of cobalt nitrate hexahydrate in 10.0 mL of water, adding 0.545g of urea, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at 90 ℃ to obtain the binderless porous ZnCo2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 4. As can be seen from fig. 4, the electrode is a porous structure composed of nanoparticles.
EXAMPLE 5 Binderless porous NiMn2O4Preparation of @ Ni electrode
(1) Dissolving 0.582 g of nickel nitrate hexahydrate and 0.716 g of manganese nitrate hydrate in 10.0 mL of water, adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at the temperature of 60 ℃ to obtain the binderless porous NiMn2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 5. As can be seen from fig. 5, the electrode has a porous structure.
Example 6A Binderless porous CoMn2O4Preparation of @ Ni electrode
(1) Dissolving 0.582 g of cobalt nitrate hexahydrate and 0.716 g of manganese nitrate hydrate in 10.0 mL of water, adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at the temperature of 60 ℃ to obtain the binderless porous CoMn2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 6. As can be seen from fig. 6, the electrode has a porous structure.
Example 7A Binderless porous ZnMn2O4Preparation of @ Ni electrode
(1) Dissolving 0.595 g of zinc nitrate hexahydrate and 0.716 g of manganese nitrate hydrate in 10.0 mL of water, then adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at 60 ℃ to obtain the porous ZnMn without the binding agent2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 7. As can be seen from fig. 7, the electrode has a porous structure.
Example 8A binderless porous MnCo2O4Preparation of @ Cu electrode
(1) Dissolving 0.358 g of hydrated manganese nitrate and 1.161 g of cobalt nitrate hexahydrate in 10.0 mL of water, then adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a piece of rectangular copper foam for 30min by using 2 mol/L hydrochloric acid, then ultrasonically cleaning by using water and ethanol, naturally airing, and then soaking the pretreated rectangular copper foam in a reaction solution;
(3) heating the reaction solution containing the copper foam in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) reaction junctionAnd after finishing, naturally cooling to room temperature, taking out the reacted foam copper, ultrasonically washing the foam copper by water and ethanol, and drying the foam copper at 90 ℃ to obtain binderless porous MnCo2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 8. As can be seen from fig. 8, the electrode has a porous structure.
Example 9A Binderless porous CuMn2O4Preparation of @ Ni electrode
(1) Dissolving 0.483 g of copper nitrate trihydrate and 0.716 g of manganese nitrate hydrate in 10.0 mL of water, adding 0.50g of glycine, and stirring to obtain a reaction solution;
(2) firstly, ultrasonically soaking a rectangular nickel foam sheet in 2 mol/L hydrochloric acid for 30min, then ultrasonically cleaning the rectangular nickel foam sheet by using water and ethanol, naturally airing the rectangular nickel foam sheet, and then soaking the rectangular nickel foam sheet subjected to pretreatment in a reaction solution;
(3) heating the reaction solution containing the foamed nickel in a heating furnace preheated at 300 ℃ until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted foam nickel, ultrasonically washing the foam nickel by water and ethanol, and drying the foam nickel at 60 ℃ to obtain the binderless porous CuMn2O4The @ Ni electrode, an SEM photograph of the electrode is shown in FIG. 9. As can be seen from fig. 9, the electrode has a porous structure.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (8)
1. Porous AB without adhesive2O4The preparation method of the @ M electrode is characterized by comprising the following specific steps of:
(1) dissolving nitrate of metal A, B in water, adding fuel and stirring to obtain reaction liquid;
(2) immersing a pretreated current collector M in the reaction solution;
(3) heating the reaction solution containing M in a preheated heating furnace until a combustion reaction occurs;
(4) after the reaction is finished, naturally cooling to room temperature, taking out the reacted current collector, and performing post-treatment to obtain the binderless porous AB2O4The @ M electrode.
2. The binderless porous AB of claim 12O4A method of manufacturing a @ M electrode, characterized in that the nitrate of the metal A, B used in step 1 is two selected from the group consisting of nickel nitrate, cobalt nitrate, copper nitrate, manganese nitrate and zinc nitrate.
3. The binderless porous AB of claim 12O4A method for preparing a @ M electrode, characterized in that the fuel used in step 1 is glycine or urea.
4. The binderless porous AB of claim 12O4A method for producing a @ M electrode, characterized in that the molar ratio of A to B in step 1 is 1: 2.
5. The binderless porous AB of claim 12O4The preparation method of the @ M electrode is characterized in that the current collector M used in the step 2 is foamed nickel, foamed copper or titanium mesh.
6. The binderless porous AB of claim 12O4The preparation method of the @ M electrode is characterized in that the pretreatment process of the current collector M used in the step 2 is that the M is ultrasonically soaked for 30min by using 2 mol/L hydrochloric acid, and then ultrasonically cleaned by using water and ethanol, and naturally dried.
7. The binderless porous AB of claim 12O4The preparation method of the @ M electrode is characterized in that the preheating temperature of the heating furnace in the step 3 is 300 ℃.
8. A process as claimed in claim 1Binderless porous AB2O4The preparation method of the @ M electrode is characterized in that the post-treatment process in the step 4 is to wash the reacted M with water and ethanol in sequence and then dry the M at 60-90 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111554516A (en) * | 2020-05-11 | 2020-08-18 | 刘庆信 | ZnCo2O4-graphene hollow microsphere supercapacitor electrode material and preparation method thereof |
| CN113546640A (en) * | 2021-07-13 | 2021-10-26 | 常州大学 | NiO-CoMn2O4Preparation method of catalyst and application of catalyst in catalytic oxidation degradation of toluene |
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| CN106024412A (en) * | 2016-07-07 | 2016-10-12 | 太原理工大学 | Carbon nanotube/metal oxide composite material with high specific capacitance feature, and preparation |
| CN106129401A (en) * | 2016-06-29 | 2016-11-16 | 北京化工大学 | A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof |
| WO2018049004A1 (en) * | 2016-09-07 | 2018-03-15 | Board Of Regents, The University Of Texas System | Flexible supercapacitors and devices containing the same |
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| CN105244181A (en) * | 2015-08-24 | 2016-01-13 | 太原理工大学 | Spinel type metal oxide of high specific capacitance and preparation and application of metal oxide |
| CN106129401A (en) * | 2016-06-29 | 2016-11-16 | 北京化工大学 | A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof |
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| CN111554516A (en) * | 2020-05-11 | 2020-08-18 | 刘庆信 | ZnCo2O4-graphene hollow microsphere supercapacitor electrode material and preparation method thereof |
| CN113546640A (en) * | 2021-07-13 | 2021-10-26 | 常州大学 | NiO-CoMn2O4Preparation method of catalyst and application of catalyst in catalytic oxidation degradation of toluene |
| CN113546640B (en) * | 2021-07-13 | 2023-10-20 | 常州大学 | NiO-CoMn 2 O 4 Preparation method of catalyst and application of catalyst in catalytic oxidative degradation of toluene |
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