CN112467077A - Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides - Google Patents
Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides Download PDFInfo
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- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003860 storage Methods 0.000 title claims abstract description 15
- 230000005611 electricity Effects 0.000 title claims abstract description 14
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 13
- 230000004048 modification Effects 0.000 title claims abstract description 12
- 238000012986 modification Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
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- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 21
- 239000007772 electrode material Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
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- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- HSQIWKNMXNBSTL-UHFFFAOYSA-J cobalt(2+);iron(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Co+2] HSQIWKNMXNBSTL-UHFFFAOYSA-J 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
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- 150000002696 manganese Chemical class 0.000 description 1
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- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
-
- 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 relates to a universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of various transition metal oxides, belonging to the technical field of production of super capacitor and alkaline secondary battery electrodes. The method is characterized in that: an electrochemical workstation is utilized to scan cyclic voltammetry curves of transition metal oxide electrode materials (including cobalt oxide, nickel cobaltate, manganese cobaltate, zinc cobaltate, cobalt nickel zinc oxide and the like) in alkaline electrolyte under a wide voltage window, so that the electrochemical activity of the electrode materials is greatly improved, and a high-performance super capacitor and an alkaline water system secondary battery are prepared. The invention adopts a simple electrochemical activation method, has simple equipment, simple operation, quick reaction and low cost, can be simultaneously used for modifying various materials, can improve the energy storage performance by more than 5 times, and has strong universality.
Description
Technical Field
The invention belongs to the technical field of production of electrodes of super capacitors and alkaline secondary batteries, and relates to a universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of various transition metal oxides.
Background
Energy is the material basis on which humans rely for survival, social and economic sustainable development. Since the 21 st century, with the increasing population, the consumption of non-renewable fossil energy sources such as coal, oil, natural gas and the like is further increased, and a global energy crisis is finally caused. Meanwhile, the combustion of these fossil fuels generates a large amount of toxic, harmful and greenhouse gases, etc., which causes serious environmental pollution problems. Therefore, the active development of renewable clean energy and the realization of efficient conversion, storage and utilization of the renewable clean energy become the key points for solving the energy crisis and promoting social progress.
Most clean energy sources such as solar energy, water energy, wind energy and the like are intermittent energy sources, so that continuous electric energy supply cannot be provided for human production and life, and advanced energy storage devices are inevitably developed. Three-position nobel chemical acquirers John b.goodenough, m.stanley Whittingham, Akira Yoshino make a great contribution in the development of lithium ion batteries, and the wide application thereof greatly improves the living standard of human beings and improves the production efficiency. However, the lithium ion batteries widely used at present still have disadvantages, such as low power density, safety hazard, high cost, insufficient life, and the like. For this reason, researchers are working on developing new energy storage devices to improve their performance and broaden the application market. For example, compared with a lithium ion battery, the super capacitor has higher power density, safety and long cycle life, so that the super capacitor has wide application prospects in the fields of national defense and military industry, aerospace, transportation, electronic information, instruments and meters and the like. Aqueous secondary batteries have higher safety and lower production costs than lithium ion batteries, making them potentially useful for large-scale energy storage applications such as power station reserve batteries. Therefore, a great deal of advanced scientific research is focused on preparing advanced supercapacitors and novel water-based secondary batteries at present, so as to further expand the application market of energy storage devices.
As a key component of the energy storage device, the reasonable selection, design and preparation of electrode materials play a decisive role in the electricity storage performance such as specific capacitance, rate capability, cycling stability and the like. Among a plurality of alternative electrode materials, transition metal (Co, Ni, Zn, Mn, V, Fe and the like) oxides have high theoretical capacitance, wide and cheap raw material sources, simple preparation (solvent hydrothermal method or annealing treatment), and various shapes (nanowires, nanorods, nanoflowers, nanosheets and the like), and are considered as ideal anode materials for assembling super capacitors and water-based secondary batteries.
Compared with powder electrode materials, the transition metal oxide array structure material directly grows on the current collector and is directly used as an electrode, the use of inactive additives such as high-molecular binder and conductive carbon black is avoided, the cost consumption is reduced, the resistance between the current collector and an active substance is also reduced, and the high-speed transmission of electrons in the active material and the current collector is facilitated. Therefore, the preparation of transition metal oxide array materials by solvothermal and one-step pyrolysis growth has become one of the mainstream research directions in this field. However, due to some defects of the metal oxide, such as low conductivity and low electrochemical reaction kinetics, the metal oxide cannot fully exert the theoretical capacitance, and the application range of the metal oxide is greatly limited. According to previous reports, the construction of multilevel nano-array structure can effectively improve the electrochemical performance of materials, for example, CoWO4/Co3O4,CoMoO4@NiCoLDH,NiCo2O4@NiO,MCo2O4@MCo2S4Composite multilevel array materials such as @ PPy (M ═ Ni, Zn) have higher specific capacitance, rate capability and cycle stability than simple array structures. However, most of the complex arrays need to be prepared by a multi-step growth method, and the reaction conditions need to be strictly controlled, so that good mutual contact interfaces between materials are ensured, and the production cost of material preparation is greatly increased. Therefore, there is an urgent need to find more efficient and low-cost methods for improving the electrochemical performance of the transition metal oxide array material.
Recent research reports indicate that the transition metal-based basic carbonate/hydroxide can be activated by an electrochemical method to realize the complication of the microstructure and the transformation of a crystal phase structure of the material, so that the electrochemical energy storage activity of the material is greatly enhanced. For example, ZHenhua Li et al can introduce rich oxygen vacancies and two-dimensional open channels in a cobalt iron hydroxide nano array by a simple cyclic voltammetry Curve (CV) scanning method, thereby greatly improving the rapid insertion/extraction capability of various transition metal ions in the array material and greatly enhancing the electricity storage performance of the material. However, all electrochemical activation methods based on CV scanning methods so far use a positive voltage window, and it is difficult to achieve electrochemical activation of transition metal oxides, mainly due to the relatively stable crystal structure of oxide materials, and the difficulty of the electrolyte to be immersed into the materials to achieve the structural transformation thereof. The only material realized is the conversion of the manganese oxide material, such as Mn reported by Charpy topic group3O4The nano wall array can be converted into Na with a complex structure by a CV activation method0.5MnO2Nanosheet array, the method still using a positive voltage window (0-1.3V vs Ag/AgCl) by long CV scans (500 cycles) and high concentration of electrolyte (10M Na)2SO4) The transformation of the material is realized. However, long CV cycles and the use of high concentrations of electrolyte will increase the production cost of the material and the method still cannot achieve electrochemical activation of other transition metal oxide materials.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of various transition metal oxides, and develops a simple, feasible, universal and universal electrochemical method to activate the transition metal oxide electrode material so as to greatly improve the electrochemical activity of the transition metal oxide electrode material, thereby assembling and preparing energy storage devices with excellent performance, such as a super capacitor, a water system secondary battery and the like.
Technical scheme
A universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of various transition metal oxides is characterized by comprising the following steps:
step 1: soaking a transition metal oxide electrode in an alkaline electrolyte potassium hydroxide (KOH);
step 2: at 10mV s in a three-electrode system-1The scanning speed of the electrode is 45 circles, CV circulation is carried out, and the scanning range of a cyclic voltammetry curve is-1-0.6V, so that an electrochemically modified transition metal oxide electrode is obtained;
the three-electrode system is: the transition metal oxide electrode is used as a working electrode, the Pt sheet is used as a counter electrode, and Hg/HgO is used as a reference electrode.
The transition metal oxide electrode material includes, but is not limited to, cobalt oxide, nickel cobaltate, manganese cobaltate, zinc cobaltate, or cobalt nickel zinc oxide.
The size of the Pt sheet is 1 multiplied by 2cm2。
The concentration of the potassium hydroxide KOH solution was 2 moles per liter.
The transition metal oxide electrode material is prepared by a hydrothermal reaction and an air annealing process.
Advantageous effects
The universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of multiple transition metal oxides provided by the invention utilizes an electrochemical workstation to perform cyclic voltammetry curve scanning on transition metal oxide electrode materials (including cobalt oxide, nickel cobaltate, manganese cobaltate, zinc cobaltate, cobalt nickel zinc oxide and the like) in an alkaline electrolyte under a wide voltage window, so that the electrochemical activity of the electrode materials is greatly improved, and a high-performance super capacitor and an alkaline water system secondary battery are prepared. The invention adopts a simple electrochemical activation method, has simple equipment, simple operation, quick reaction and low cost, can be simultaneously used for modifying various materials, can improve the energy storage performance by more than 5 times, and has strong universality.
In the invention, the transition metal oxygen is prepared by using a conventional hydrothermal/solvothermal method and a one-step pyrolysis methodPreparing a material array, and directly soaking the prepared transition metal oxide electrode in alkaline electrolyte (2M KOH) at 10mV s in a three-electrode system-1The scanning speed of the method runs for 45 CV cycles, a wide voltage window range is used for enabling the CV cycles to span positive and negative potentials, and irreversible electrochemical reaction of transition metal under the wide voltage window cycle is mainly utilized for promoting the reconstruction of the morphology and the structure of the material so as to realize the transformation of the microscopic morphology and the structure of the oxide material.
The invention adopts a simple electrochemical activation method, has simple equipment, simple operation, quick reaction and low cost, and can be simultaneously used for modifying various materials. Through comparison before and after activation, the appearance and the surface atomic structure of the material are changed violently, and electrochemical performance tests show that the specific capacitance of the electrode material can be improved by more than 5 times, and the rate capability and the cycle stability can be greatly enhanced. For example, by electrochemically activated Ni-Co oxide (NiCoO) nanowire array, the surface of the nanowire forms a compact secondary nano microstructure, the valence states of Ni and Co elements on the surface also change dramatically, and due to the structural change, the activated electrode is at 0.5A g-1175.5mAh g was obtained at the current density-1A large specific capacitance value which is increased by 5.45 times compared with the material before activation; and still exhibits extremely excellent performance under high current charging and discharging (at 100A g)-1The lower level still reaches 99.1mAh g-1) Also superior to the electrode before activation; in addition, the activated NiCoO composite nanowire array has extremely excellent high-current charge-discharge long-cycle stability (>10000 turns, 50A g-1Below). Further experiments show that the method has extremely strong universality and can be used for carrying out electrochemical activation on various transition metal oxide materials, such as cobalt oxide, nickel cobaltate, manganese cobaltate, zinc cobaltate, cobalt molybdate, cobalt-nickel-zinc oxide and the like.
The appearance structure of the transition metal oxide electrode activated by the electrochemical method is changed violently, the electrochemical activity is greatly improved, and the specific capacitance performance is improved by more than 5 times.
The material modified by the electrochemical method can be used for a super capacitor and an alkaline secondary battery to obtain high energy storage performance.
Drawings
FIG. 1: CV cycle curves during electrochemical activation of nickel cobaltate nanowire arrays grown on nickel foam substrates.
FIG. 2: scanning electron microscope picture of nickel cobaltate nanowire array growing on foamed nickel substrate
FIG. 3: scanning electron microscope picture of product obtained after activation of nickel cobaltate nanowire array grown on foamed nickel substrate by electrochemical CV method
FIG. 4: comparison of specific capacitance values of nickel cobaltate precursor arrays (NiCoOH), nickel cobaltate nanowire arrays (NiCoO) and electrochemically activated nickel cobaltate nanowire arrays (NiCoO-ac) grown on foamed nickel substrates
FIG. 5: the nickel cobaltate nanowire array activated by the electrochemical method is 50A g-1Long cycle stability test results under charge-discharge current density
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
preparation of electrode material
Example 1: a method for preparing an array of electrochemically activated nickel cobaltate (NiCoO) nanowires, comprising the steps of: nickel cobaltate nanowire arrays (NiCoO NWAs) are prepared by a simple hydrothermal reaction and air annealing process. First, 10mM nickel nitrate hexahydrate (Ni (NO)3)2·6H2O, AR), 20mM cobalt nitrate hexahydrate (Co (NO)3)2·6H2O, AR) and 20mM Urea (CO (NH)2)2AR) was dissolved in 15mL of ultrapure water (18.2 M.OMEGA.cm) to prepare a uniform solution. The solution was then transferred to a 20mL Teflon lined steel autoclave and then dipped into a block of nickel foam (1X 4 cm)2) The nickel foam was previously washed with 0.1M hydrochloric acid, acetone, ethanol and deionized water. After maintaining the autoclave in an oven at 120 ℃ for 10 hours, the autoclave was taken out and naturally cooled. The final product was removed, sonicated in deionized water for 2 minutes, and then rinsed with copious amounts of deionized water to remove loose particles and residues from the surfaceA compound (I) is provided. The washed product was dried in air at 70 ℃ for 10 hours. Finally, the prepared precursor array was placed in a muffle furnace at 5 ℃ for min-1The temperature rise speed of the catalyst is calcined in air at 350 ℃ for 30 minutes, and then the catalyst is naturally cooled to obtain NiCoO NWAs. 3) Finally, electrochemical activation is carried out, NiCoO NWAs is used as a working electrode, and a Pt sheet (1X 2 cm)2) As counter electrode, Hg/HgO as reference electrode, in 2M KOH electrolyte at 10mV s-1The scanning speed of the nano-composite array is 45 circles of CV under a voltage window of-1.0V to 0.6V, and an activated sample NiCoO NWAs-ac nano-composite array is obtained.
Example 2: a method for preparing an array of electrochemically activated NiCoO nanoplates, comprising the steps of: 1) first, nickel cobalt double hydroxide was prepared and 40mM 2-methylimidazole (MIM) methanol solution was added to another solution containing 10mM Ni (NO) under magnetic stirring3)2·6H2O and 10mM Co (NO)3)2·6H2O in methanol. On the basis, the reaction solution is put into a tetrafluoroethylene lined stainless steel reaction kettle, and a carbon fiber cloth growth substrate (CFC, 1 multiplied by 4 cm) which is cleaned in advance is added at the same time2) The solvothermal reaction was carried out at 140 ℃ for 14h, after the reaction was complete the sample was rinsed with methanol and dried in an air oven at 70 ℃. 2) Then preparing nickel cobalt oxide, putting the dried sample into a tube furnace, annealing for 30min at 350 ℃ in the air, and programming the temperature for 5 ℃ for min-1And obtaining the NiCoO nanosheet array. 3) Finally, carrying out electrochemical activation, wherein the NiCoO nanosheet array is used as a working electrode, and a Pt sheet (1 multiplied by 2 cm)2) As counter electrode, Hg/HgO as reference electrode, in 2M KOH electrolyte at 10mV s-1The sweep rate of (A) was 45 cycles of CV sweeping over a voltage window of-1.0V to 0.6V, yielding an activated sample NiCoO-ac nanocomposite array.
Example 3: a method for preparing an array of electrochemically activated zinc cobaltate (ZnCoO) nanowires, comprising the steps of: 1) zinc nitrate hexahydrate (Zn (NO) was used at 25mM3)2·6H2O, AR) and 25mM cobalt nitrate hexahydrate (Co (NO)3)2·6H2O, AR) as metal cation precursor, 15mM NH4F and 25mM CO (NH)2)2As a baseAnd (3) a sexual source, namely pouring the solution containing the alkali source into the solution containing the metal ions, and uniformly stirring for 10 min. The reaction solution was then transferred to a 20mL Teflon lined steel autoclave while immersed in a block of foamed nickel substrate (1X 4 cm)2) The nickel foam was previously washed with 0.1M hydrochloric acid, acetone, ethanol and deionized water. After maintaining the autoclave in an oven at 120 ℃ for 10 hours, the autoclave was taken out and naturally cooled. 2) The nickel foam was taken out, rinsed three times with ultrapure water, placed in a vacuum drying oven and dried at 70 ℃ for 8 hours. Finally, the prepared precursor array is placed in a muffle furnace for 5 ℃ min-1The temperature is raised to 350 ℃ at the temperature raising speed and maintained for 30 minutes, and then the temperature is naturally lowered to obtain the ZnCoO nanowire array. 3) Electrochemical activation: ZnCoO nanowire array as working electrode, Pt sheet (1 x 2 cm)2) As counter electrode, Hg/HgO as reference electrode, in 2M KOH electrolyte at 10mV s-1The sweep speed of the array is swept for 45 cycles of CV under a voltage window of-1.0V to 0.6V, and an ac-ZnCoO nano composite array of an activated sample is obtained.
Example 4: a method for preparing an array of electrochemically activated manganese cobaltate (MnCoO) nanowires, comprising the steps of: 1) with 10mM cobalt nitrate hexahydrate (Co (NO)3)2·6H2O, AR) and 5mM manganese sulfate monohydrate (Mn (SO)4)·H2O, AR) as a source of metal cations. 150mM NH was used4F and 90mM CO (NH)2)2As an alkaline source, a solution containing the alkaline source is poured into a solution containing metal ions, and the solution is stirred uniformly for 10 min. The solution was then transferred to a 20mL Teflon lined steel autoclave and immersed in a block of foamed nickel base (1X 4 cm)2) The nickel foam was previously washed with 0.1M hydrochloric acid, acetone, ethanol and deionized water. Finally, the mixture is put into an oven at 120 ℃ and maintained for 8 hours. After the reaction is finished, the foamed nickel is taken out, washed with ultrapure water for three times and then placed into a vacuum drying oven at 70 ℃ for 8 hours. After drying, the prepared precursor array was placed in a muffle furnace at 5 ℃ for min-1The temperature is raised to 350 ℃ at the temperature raising speed and maintained for 30 minutes to obtain the MnCoO nanowire array. 3) Electrochemical activation: MnCoO nanowire array as working electrode, Pt sheet (1 × 2 cm)2) As a counter electrode, Hg/HgO as a reference electrode, in 2M KOH electrolyte at 10mV s-1Sweeping the sample for 45 CV cycles under a voltage window of-1.0V to 0.6V to obtain an activated sample ac-MnCoO nano composite array.
Second, electrochemical performance test
And (3) electrochemical performance testing: the standard three-electrode test system is selected for test, the synthetic material is used as the working electrode, and the platinum foil (1 multiplied by 2 cm)2) For the counter electrode, a standard Hg/HgO electrode was used as the reference electrode and the electrolyte was 2.0M KOH aqueous solution. The electrochemical property changes of the transition metal oxide before and after electrochemical activation are comprehensively compared by testing Cyclic Voltammetry (CV) curves, constant current charging and discharging (GCD) and alternating current impedance spectroscopy (EIS) of the sample before and after electrochemical activation.
Taking the electrochemically activated NiCoO nanowire array synthesized in example 1 as an example, it can be seen from fig. 1 that as the CV cycle increases, the response current corresponding to the positive voltage interval increases, which means the electrochemical energy storage performance is enhanced. Through fig. 2 and fig. 3, it is found that the NiCoO nanowires after electrochemical activation are transformed into a core-shell multi-level nanocomposite structure. Further specific capacitance comparison indicates (fig. 4) that the specific capacitance of the electrochemically activated electrode is greatly improved, at 0.5A g, compared to the precursor hydroxide nanowire array and the electrochemically activated NiCoO nanowire array-1The charge-discharge current density reaches 175.5mAh g-1At 100A g-1Still reaches 175.5mAh g-1And excellent high-rate charge and discharge performance is shown. Finally, FIG. 5 shows that the NiCoO nanowire array after activation is at 50A g-1The service life of the large-current charging and discharging test reaches more than 10000 circles, and the method has great practical application potential. Other transition metal oxide materials have similar morphology change and performance enhancement effects after being electrochemically activated, and are not described in detail herein.
Claims (5)
1. A universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of various transition metal oxides is characterized by comprising the following steps:
step 1: soaking a transition metal oxide electrode in an alkaline electrolyte potassium hydroxide (KOH);
step 2: at 10mV s in a three-electrode system-1The scanning speed of the electrode is 45 circles, CV circulation is carried out, and the scanning range of a cyclic voltammetry curve is-1-0.6V, so that an electrochemically modified transition metal oxide electrode is obtained;
the three-electrode system is: the transition metal oxide electrode is used as a working electrode, the Pt sheet is used as a counter electrode, and Hg/HgO is used as a reference electrode.
2. The universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of multiple transition metal oxides as claimed in claim 1, wherein: the transition metal oxide electrode material includes, but is not limited to, cobalt oxide, nickel cobaltate, manganese cobaltate, zinc cobaltate, or cobalt nickel zinc oxide.
3. The universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of multiple transition metal oxides as claimed in claim 1, wherein: the size of the Pt sheet is 1 multiplied by 2cm2。
4. The universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of multiple transition metal oxides as claimed in claim 1, wherein: the concentration of the potassium hydroxide KOH solution was 2 moles per liter.
5. The universal electrochemical modification preparation method for effectively enhancing the electricity storage performance of multiple transition metal oxides as claimed in claim 1, wherein: the transition metal oxide electrode material is prepared by a hydrothermal reaction and an air annealing process.
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