CN115346806A - Preparation method of supercapacitor electrode material based on cobalt-iron-manganese compound - Google Patents
Preparation method of supercapacitor electrode material based on cobalt-iron-manganese compound Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XHASLETWXKYQSC-UHFFFAOYSA-N cobalt iron manganese Chemical compound [Mn][Fe][Fe][Co] XHASLETWXKYQSC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
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- 150000002736 metal compounds Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000005695 Ammonium acetate Substances 0.000 claims description 9
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 9
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 239000002110 nanocone Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims 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 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
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- 229910020598 Co Fe Inorganic materials 0.000 description 11
- 229910002519 Co-Fe Inorganic materials 0.000 description 11
- 238000004070 electrodeposition Methods 0.000 description 11
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- CHZUADMGGDUUEF-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2] CHZUADMGGDUUEF-UHFFFAOYSA-N 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound, which comprises the steps of sequentially ultrasonically cleaning foamed nickel in hydrochloric acid, acetone, absolute ethyl alcohol and deionized water, then drying, placing the cleaned and dried foamed nickel in a reaction kettle filled with a prepared precursor solution, and carrying out hydrothermal reaction to obtain a precursor electrode of a binary metal compound; the preparation method is simple, the used raw materials are rich in yield and low in price, the prepared electrode exposes rich active sites and has the characteristics of high catalytic activity and high structural stability, multiple redox reactions can occur inside the electrode due to rich ionic valence states, an ion transmission channel is increased under the synergistic action of multiple ions, the conductivity is enhanced, and the microstructure is improved, so that the electrode material with excellent electrochemical performance is realized.
Description
Technical Field
The invention belongs to the technical field of supercapacitor electrode materials, and particularly relates to a preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a battery, has the advantages of high power density of the traditional capacitor and high energy density of a secondary battery, and has the advantages of high charging speed, long cycle life and no pollution to the environment. In view of various performance advantages, the super capacitor can be widely applied to a plurality of fields such as automobile industry, aerospace, national defense science and technology, information technology, electronic industry and the like, and belongs to a standard full-series low-carbon economic core product.
Energy density and power density are main indexes for measuring the performance of the super capacitor, and the properties of the electrode material are key factors for determining the electrochemical performance of the capacitor, such as energy density, power density and the like.
Materials for supercapacitors mainly include carbon-based materials (activated carbon, carbon nanotubes, carbon aerogel, graphene), transition metal (hydro) oxides and conductive polymers. Among them, the transition metal (hydr) oxide has advantages of good conductivity and large specific capacity, but the cycle stability is not ideal. Therefore, it is very necessary to introduce different electrode materials for compounding to develop a supercapacitor electrode material having excellent capacitance, stability and cyclicity.
The patent documents relevant to the present application are found by searching, and the specific disclosures are as follows:
1. a preparation method of a carbon nano tube-graphene supercapacitor composite electrode material (CN 103824704B);
2. a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene (CN 113593931B);
3. a preparation method of an electrode material with a cobalt manganate/nickel sulfide core-shell array structure (CN 111986929A);
the research on the electrode materials still has the problems of low rate performance, poor cycle stability and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound, which can obviously improve the electrochemical activity, high speed performance and strong cycling stability of the material.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound comprises the following steps:
1) Cleaning the substrate;
the method comprises the steps of adopting foamed nickel as a substrate material, respectively washing the foamed nickel with hydrochloric acid for 15 minutes under ultrasonic washing, then washing with deionized water, then washing with acetone for 20 minutes, then washing with deionized water, washing with ethanol for 10 minutes, then washing with deionized water for three times, and finally drying at 60 ℃. Obtaining clean foam nickel;
2) The preparation method of the electrode material with the nanometer cone-shaped precursor Co-Fe-CH nanometer cone-shaped structure by using the foamed nickel as the substrate comprises the following hydrothermal reaction steps:
(1) Dissolving cobalt nitrate, ammonium acetate, urea and ferric chloride in 40ml of deionized water, and stirring the solution for 20 minutes under a constant magnetic stirrer to obtain a dispersion liquid; the precursor solution is prepared from the following components in percentage by weight: the ferric chloride is 2:1, the catalyst is urea and ammonium acetate;
(2) Transferring the foamed nickel and the dispersion prepared in the step (1) into a 50mL polytetrafluoroethylene lining autoclave, putting the autoclave into a drying oven, and reacting at 120 ℃ for 12 hours; after the hydrothermal reaction is finished, naturally cooling to room temperature, respectively washing the obtained Co-Fe-CH precursor on the basis of the foamed nickel by using deionized water and ethanol for three times in an ultrasonic cleaning machine, and carrying out vacuum drying for 5 hours at the temperature of 60 ℃ to obtain the precursor Co-Fe-CH electrode material with the foamed nickel as the substrate and having the nanometer cone-shaped structure;
3) Preparing an electrode material of a Co-Fe-Mn ternary metal compound with foamed nickel as a substrate;
taking an electrode material of a precursor Co-Fe-CH nano cone structure with foamed nickel as a substrate as a working electrode, a platinum sheet as a counter electrode and saturated Ag/AgCl as a reference electrode; containing Co (NO 3) 2.6H 2 O and MnCl 2 ·4H 2 The O mixed aqueous solution is used as an electrolyte for deposition, the deposition technology adopts cyclic voltammetry, the sweep rate is 5mV/s under the constant voltage window of-1.2V-0.2V, the scanning is carried out for 15 circles, the electrode is repeatedly washed with deionized water for three times, and the electrode is placed in a vacuum drying oven to be dried overnight at the temperature of 60 ℃ to obtain the electrode material of the cobalt-iron-manganese ternary metal compound;
4) And characterizing the morphology of the electrode material of the cobalt-iron-manganese ternary metal compound through SEM, TEM and XRD.
In addition, the ultrasonic power of the ultrasonic cleaning in the step 1) is 360W, and the drying treatment is vacuum drying.
And the drying oven in the step 2) is an air-blast drying oven, and the temperature rise speed is 7 ℃ per minute.
And the step 3) is to perform electrochemical deposition of Mn element on the electrode material with the precursor Co-Fe-CH nano cone structure through a three-electrode electrochemical workstation.
And, contains Co (NO 3) 2.6H 2 O and MnCl 2 ·4H 2 Co (NO 3) 2.6H in O mixed aqueous solution 2 The concentration of O is 1mmol; mnCl 2 ·4H 2 The concentration of O was 1mmol.
And the electrode material of the Co-Fe-Mn ternary metal compound taking the foamed nickel as the substrate is used as the electrode material of the super capacitor.
The invention has the advantages and positive effects that:
the invention selects high-conductivity foamed nickel as a substrate, prepares the Fe-doped Co-Fe electrode through one-step hydrothermal reaction, when not doped with Fe, the single Co electrode is in a structure of a long nanowire on a nanosheet, and when the Co-Fe binary metal electrode is in a nanocone structure after being doped with Fe, the Fe doping obviously changes the compound synthesisThe morphology structure of the electrode; in the aspect of electrochemical performance, the specific capacity of the Co-Fe electrode area is 10mA/cm 2 The lower is 3 to 4F/cm 2 Is obviously higher than that of the Co electrode under the same current density by 1-2F/cm 2 And shows better circulation stable life (the current density is 20 mA/cm) 2 The time is 6000s, and the temperature is kept more than 80 percent).
In order to further improve the electrochemical performance in other aspects, electrochemical deposition is carried out on the basis of a precursor Co-Fe to prepare a ternary metal compound Co-Fe-Mn electrode, compared with the Co-Fe electrode, the electrode appearance has more gaps among nanocones on a framework, more ion channels are established, the example transmission is convenient, and the current capacity is 10mA/cm 2 The specific capacity per hour area is high by 7 to 8F/cm 2 The electrochemical property is improved by influencing the shape of the material after electrochemical deposition of Mn element, and in addition, a quasi-solid asymmetric super capacitor device is assembled by taking a ternary metal Co-Fe-Mn electrode as a positive electrode, and the power density is 9-10 mW/cm 2 The lower part is higher than 0.353mW/cm 2 The energy density of (2).
The work proves that the multi-element metal compound electrode is prepared through doping and electrochemical deposition, due to rich ionic valence states, various redox reactions can occur inside the multi-element metal compound electrode, an ion transmission channel is increased under the synergistic effect of various ions, the conductivity is enhanced, the microstructure is improved, and therefore the electrode material with excellent electrochemical performance is achieved, and therefore the construction of the ternary metal electrode material has wide application prospects in the aspect of high-performance energy storage devices.
Drawings
Fig. 1 is a SEM image of the surface of the precursor electrode. The SEM image shows that after the iron doping treatment, the material grows into a nanorod morphology structure;
FIG. 2 is an SEM image of the surface of an electrode after electrochemical deposition, and it can be seen from the SEM image that after electrochemical deposition treatment is performed on the basis of a precursor, the material grows into a nanorod morphology structure;
FIG. 3 is an SEM image of the surface of an electrode after electrochemical deposition, and it can be seen from the SEM image that after electrochemical deposition treatment is performed on the basis of a precursor, the material grows to have a nanosheet morphology structure;
fig. 4 is a precursor electrode XRD pattern. As can be seen from the figure, after the iron doping treatment, the generated bicarbonate oxide corresponds to the standard card;
FIG. 5 is a comparison graph of the electrochemical properties of the generated electrode material GCD by adjusting the reaction temperature in the hydrothermal reaction process under the condition that other reaction conditions are kept unchanged;
FIG. 6 is a comparison graph of the electrochemical performance of the electrode material GCD produced by adjusting the iron-doping amount in the hydrothermal reaction process under the condition that other reaction conditions are kept unchanged.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Example 1
A preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound comprises the following steps:
step one, substrate cleaning:
the method adopts foamed nickel as a substrate material, and the surface of the foamed nickel is 3cm 2 The length is 3cm and the width is 1 cm; the foamed nickel is respectively washed by 3mol/L hydrochloric acid for 15 minutes under the action of ultrasonic waves, then washed by deionized water, washed by acetone for 20 minutes, washed by deionized water, washed by ethanol for 10 minutes, washed by deionized water for three times to remove pollutants and surface oxidation layers, and finally dried in a vacuum drying oven at 60 ℃. Obtaining clean foam nickel;
wherein the ultrasonic power of the ultrasonic cleaning is 360W, the drying treatment is vacuum drying,
step two, preparing a precursor Co-Fe hydrogen carbonate oxide nano-rod or nano-sheet electrode material with a nano-cone structure and taking foamed nickel as a substrate:
the method comprises the following steps:
(1) Dissolving cobalt nitrate hexahydrate, ammonium acetate, urea and ferric chloride hexahydrate in 40ml of deionized water, and stirring the solution for 20 minutes under a constant magnetic stirrer to obtain a dispersion liquid; the precursor solution is prepared from cobalt nitrate hexahydrate: ferric chloride hexahydrate is 2:1, the catalyst is urea and ammonium acetate; wherein the content of ferric chloride hexahydrate is 0.5ml; the cobalt nitrate hexahydrate is 0.29g/mmol; ammonium acetate 0.231g/3mmol; 0.6007g of urea;
(2) Transferring the foamed nickel and the dispersion liquid prepared in the step (1) into a 50mL polytetrafluoroethylene lining autoclave, putting the autoclave into a drying oven, and reacting at the hydrothermal reaction temperature of 120 ℃ for 12 hours; after the hydrothermal reaction is finished, naturally cooling to room temperature, respectively washing the obtained Co-Fe-CH precursor on the basis of the foamed nickel by using deionized water and ethanol for three times in an ultrasonic cleaning machine, and carrying out vacuum drying for 5 hours at the temperature of 60 ℃ to obtain the precursor Co-Fe-CH electrode material with the foamed nickel as the substrate and having the nanometer cone-shaped structure; wherein the drying oven is a blast drying oven, and the heating speed is 7 ℃ per minute;
step three, preparing the electrode material of the Co-Fe-Mn ternary metal compound taking the foamed nickel as the substrate
Electrochemically depositing Mn element on the electrode material of the precursor Co-Fe-CH nano cone structure through a three-electrode electrochemical workstation; is operated as
Taking an electrode material of a precursor Co-Fe-CH nano cone-shaped structure with foamed nickel as a substrate as a working electrode, a platinum sheet as a counter electrode and saturated Ag/AgCl as a reference electrode; 1mmol Co (NO 3) 2.6H 2 O and 1mmol MnCl 2 ·4H 2 O is put in 40ml deionized water, and then stirred for 20min by a magnetic stirrer until the solution is light pink transparent liquid, the mixed aqueous solution is used as electrolyte for deposition, the deposition technology adopts cyclic voltammetry, the sweep rate is 5mV/s under the constant voltage window of-1.2V to 0.2V, scanning is carried out for 15 circles, the solution is repeatedly washed for three times by deionized water, and the solution is put in a vacuum drying oven to be dried overnight at 60 ℃ to obtain the electrode material of the cobalt-iron-manganese ternary metal compound; the prepared Co-Fe-Mn loading capacity is 2.71mg/cm 2 。
And step four, characterizing the morphology of the electrode material of the cobalt-iron-manganese ternary metal compound through SEM, TEM and XRD.
Example 2
In the embodiment, variable regulation and control are carried out on the duration and the temperature of the hydrothermal reaction treatment, and the optimal experimental conditions are selected according to the final performance of the obtained foamed nickel electrode;
referring to the preparation process of example 1, hydrothermal reaction was carried out at 100 ℃ and 140 ℃, a precursor electrode was prepared under the condition that other conditions were kept unchanged (compound raw materials were cobalt nitrate, ferric chloride, urea, and ammonium acetate, the reaction time was 12 hours, and the temperature rise rate was 7 ℃ per minute), and the relationship between the electrode performance and the hydrothermal reaction temperature was studied. As can be seen from FIG. 5, the samples treated by the hydrothermal reaction at 120 ℃ have electrochemical properties similar to those of the samples treated by the hydrothermal reaction at 140 ℃, and therefore, the hydrothermal reaction temperature at 120 ℃ is determined to be most suitable. Not only meets the requirement of high electrochemical performance, but also avoids the complicated procedure of over-long heating time. The reaction time is saved, and the experimental process is simplified.
Example 3
In the embodiment, the optimal experimental conditions are selected according to the final performance of the obtained foam nickel electrode by performing variable regulation and control on the addition amount of the iron element.
Referring to the preparation process of example 1, 0mml of ferric chloride, 0.15mml of ferric chloride, 0.75mmol of ferric chloride and 1mmol of ferric chloride are respectively used for hydrothermal reaction, a precursor electrode is prepared under the condition that other conditions are kept unchanged, and the relation between the electrode performance and the doping amount of the raw material ferric chloride is studied. As can be seen from FIG. 6, under the condition that other conditions are kept unchanged (the compound raw materials are cobalt nitrate, ferric chloride, urea and ammonium acetate, the reaction time is 12 hours, the reaction temperature is 120 ℃, the temperature rise rate is 7 ℃ per minute), the sample treated by the reaction of 0.5mmol of ferric chloride has the optimal electrochemical performance, and therefore, the optimum doping amount of 0.5mmol of ferric chloride is determined. Not only meets the requirement of high electrochemical performance, but also avoids the complex operation of weighing a large amount of medicines. The using amount of the medicine is saved, and the production cost is reduced.
The invention selects high-conductivity foamed nickel as a substrate, prepares the Fe-doped Co-Fe electrode through one-step hydrothermal reaction, wherein the single Co electrode is in a structure of a long nanowire on a nanosheet when Fe is not doped, and the Co-Fe binary metal electrode after Fe doping is a nanoconeThe structure, therefore, the Fe doping obviously changes the shape and structure of the compound synthesis electrode; in the aspect of electrochemical performance, the specific capacity of the Co-Fe electrode area is 10mA/cm 2 The lower is 3-4F/cm 2 Is obviously higher than 1-2F/cm of Co electrode under the same current density 2 And shows better cycle stability life (the current density is 20 mA/cm) 2 The time is 6000s, and the temperature is kept more than 80 percent).
In order to further improve the electrochemical performance in other aspects, electrochemical deposition is carried out on the basis of a precursor Co-Fe to prepare a ternary metal compound Co-Fe-Mn electrode, compared with the Co-Fe electrode, the electrode appearance has more gaps among nanocones on a framework, more ion channels are established, the example transmission is convenient, and the current capacity is 10mA/cm 2 The specific capacity per hour area is high by 7 to 8F/cm 2 The electrochemical property is improved by influencing the shape of the material after electrochemical deposition of Mn element, and in addition, a quasi-solid asymmetric super capacitor device is assembled by taking a ternary metal Co-Fe-Mn electrode as a positive electrode, and the power density is 9-10 mW/cm 2 Lower than 0.353mW/cm 2 The energy density of (2).
The work proves that the multi-element metal compound electrode is prepared through doping and electrochemical deposition, due to rich ionic valence, multiple redox reactions can occur inside the multi-element metal compound electrode, an ion transmission channel is increased under the synergistic effect of multiple ions, the conductivity is enhanced, the microstructure is improved, and therefore the electrode material with excellent electrochemical performance is realized, and the construction of the ternary metal electrode material has wide application prospect in the aspect of high-performance energy storage devices.
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and appended claims, and therefore, the scope of the invention is not limited to the disclosure of the embodiments and drawings.
Claims (6)
1. A preparation method of a supercapacitor electrode material based on a cobalt-iron-manganese compound is characterized by comprising the following steps:
1) Cleaning the substrate;
the method comprises the steps of adopting foamed nickel as a substrate material, respectively washing the foamed nickel with hydrochloric acid for 15 minutes under ultrasonic washing, then washing with deionized water, then washing with acetone for 20 minutes, then washing with deionized water, washing with ethanol for 10 minutes, then washing with deionized water for three times, and finally drying at 60 ℃. Obtaining clean foam nickel;
2) The preparation method of the electrode material with the nanometer cone-shaped precursor Co-Fe-CH nanometer cone-shaped structure by using the foamed nickel as the substrate comprises the following hydrothermal reaction steps:
(1) Dissolving cobalt nitrate, ammonium acetate, urea and ferric chloride in 40ml of deionized water, and stirring the solution for 20 minutes under a constant magnetic stirrer to obtain a dispersion liquid; the precursor solution is prepared from the following components in percentage by weight: the ferric chloride is 2:1, the catalyst is urea and ammonium acetate;
(2) Transferring the foamed nickel and the dispersion prepared in the step (1) into a 50mL polytetrafluoroethylene lining autoclave, putting the autoclave into a drying oven, and reacting at 120 ℃ for 12 hours; after the hydrothermal reaction is finished, naturally cooling to room temperature, respectively washing the obtained Co-Fe-CH precursor on the basis of the foamed nickel by using deionized water and ethanol for three times in an ultrasonic cleaning machine, and carrying out vacuum drying for 5 hours at the temperature of 60 ℃ to obtain the precursor Co-Fe-CH electrode material with the foamed nickel as the substrate and having the nanometer cone-shaped structure;
3) Preparing an electrode material of a Co-Fe-Mn ternary metal compound with foamed nickel as a substrate;
taking an electrode material of a precursor Co-Fe-CH nano cone-shaped structure with foamed nickel as a substrate as a working electrode, a platinum sheet as a counter electrode and saturated Ag/AgCl as a reference electrode; containing Co (NO 3) 2.6H 2 O and MnCl 2 ·4H 2 The O mixed aqueous solution is used as an electrolyte for deposition, the deposition technology adopts cyclic voltammetry, the sweep rate is 5mV/s under the constant voltage window of-1.2V-0.2V, the scanning is carried out for 15 circles, the electrode is repeatedly washed with deionized water for three times, and the electrode is placed in a vacuum drying oven to be dried overnight at the temperature of 60 ℃ to obtain the electrode material of the cobalt-iron-manganese ternary metal compound;
4) And characterizing the morphology of the electrode material of the cobalt-iron-manganese ternary metal compound through SEM, TEM and XRD.
2. The preparation method of the cobalt-iron-manganese compound-based supercapacitor electrode material according to claim 1, characterized in that: the ultrasonic power of the ultrasonic cleaning in the step 1) is 360W, and the drying treatment is vacuum drying.
3. The preparation method of the cobalt-iron-manganese compound-based supercapacitor electrode material according to claim 1, characterized in that: the drying oven in the step 2) is an air blowing drying oven, and the temperature rise speed is 7 ℃ per minute.
4. The preparation method of the supercapacitor electrode material based on the cobalt-iron-manganese compound according to claim 1, wherein the preparation method comprises the following steps: and 3) electrochemically depositing Mn element on the electrode material of the precursor Co-Fe-CH nano cone structure through a three-electrode electrochemical workstation.
5. The preparation method of the cobalt-iron-manganese compound-based supercapacitor electrode material according to claim 1, characterized in that: containing Co (NO 3) 2.6H 2 O and MnCl 2 ·4H 2 Co (NO 3) 2.6H in O mixed aqueous solution 2 The concentration of O is 1mmol; mnCl 2 ·4H 2 The concentration of O was 1mmol.
6. Use of a cobalt iron manganese ternary metal compound electrode material prepared according to any of the methods of claims 1 to 5, characterized in that: the material is used as an electrode material of a super capacitor.
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