CN106637332A - Method for preparing cathode material AgCuO2 through anodic oxidation electrodeposition - Google Patents

Method for preparing cathode material AgCuO2 through anodic oxidation electrodeposition Download PDF

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Publication number
CN106637332A
CN106637332A CN201611049774.9A CN201611049774A CN106637332A CN 106637332 A CN106637332 A CN 106637332A CN 201611049774 A CN201611049774 A CN 201611049774A CN 106637332 A CN106637332 A CN 106637332A
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conductive glass
electro
electrode
agcuo
agcuo2
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CN201611049774.9A
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CN106637332B (en
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刘润
芦琴燕
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • 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
    • 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
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • 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

Abstract

The invention discloses a method for preparing cathode material AgCuO2 through anodic oxidation electrodeposition. The method is characterized in that in strong alkaline mixed electrolyte, ammonia water and Ag + are complexed and ammonia water and Cu2 + are complexed through an anodic electrodeposition method, constant current electrodeposition is carried out in a water bath at the temperature of 40 DEG C, an AgCuO2 thin film electrode which has the sheet-like morphology and is deposited on ITO conductive glass is obtained in a short period of time, and then tests of X-ray powder diffraction, field emission scanning electron microscopy representation and a discharging experiment in an alkaline solution are conducted on the deposited AgCuO2 thin film electrode. The method has the beneficial effects that the used raw materials are low in cost, equipment is simple, operation is easy, convenient and fast, and meanwhile the environmental friendliness is achieved.

Description

One kind prepares cathode material AgCuO by anodic oxidation electro-deposition2Method
Technical field
The present invention relates to one kind prepares cathode material AgCuO by anodic oxidation electro-deposition2Method, belong to without electromechanics Pole material preparation process technical field.
Background technology
AgCuO2It is a kind of material in layered crystal structure, there is the phenomenon of electric charge delocalization, part Cu between its each atom The special valence state of presentation+trivalent, thus, it is also a kind of preferable electrode material of electric conductivity, the charge-discharge velocity with superelevation, 29 seconds can be smaller than as the cathode material of alkaline secondary cell, discharge and recharge time.
So far, AgCuO2Preparation be mainly by precursor A g2Cu2O3Carry out chemical oxidation (ozone, over cure Hydrochlorate etc.) or electrochemical oxidation obtain, it is therefore desirable to first prepare precursor A g2Cu2O3, reoxidize and obtain product AgCuO2, so And, by anodic electrodeposition from corresponding salt AgNO3、Cu(NO3)2A direct step obtains AgCuO2Method have not been reported.
The content of the invention
Present invention aims to the shortcoming and defect of prior art, there is provided a kind of simple and effective by anodic oxygen Chemical/electrodeposition is preparing cathode material AgCuO2Method.
Cathode material AgCuO is prepared by anodic oxidation electro-deposition2Method the step of it is as follows：
1) working electrode, the i.e. activation of ITO electro-conductive glass：ITO electro-conductive glass 3～5 times is cleaned with acetone, then deionized water will Electro-conductive glass is placed on 30～60min of cleaning in ultrasonic cleaner, then electro-conductive glass is placed in dilute nitric acid solution and activates 30 ～60s, last deionized water cleaning is standby；
2)AgCuO2The preparation of membrane electrode：By the AgNO of 0.000375mol3With the Cu (NO of 0.0003mol3)2·3H2O is in one Stirring and dissolving in quantitative distilled water, is added dropwise over the NH of 0.05mol in stirring3, it is allowed to and Ag+And Cu2+Fully it is complexed to solution Shape is clarified in navy blue, adds 0.025mol NaOH solutions to adjust the pH of solution afterwards, finally added distilled water and obtain volume and be The clarification electrolyte of 100mL；With ITO electro-conductive glass as working electrode, platinum plate electrode is that, to electrode, silver-silver chloride electrode is ginseng Than electrode, being placed in electrolyte carries out galvanostatic deposition, and electro-deposition gained sample deionized water is dried naturally after rinsing, and is obtained Black AgCuO based on ITO electro-conductive glass2Film.
40 DEG C of bath temperature is tested during described galvanostatic deposition, it is 0.1A to apply anode constant current, and sedimentation time is 1000～3000s.
The experimental technique of anodic electrodeposition is present invention employs, by applying suitable experiment condition, has obtained stable AgCuO with sheet-like morphology2Film crystal, experimental facilities is simple, under quick, normal temperature and pressure easy to operate in same solution i.e. Can carry out.The present invention also has low cost, eco-friendly advantage, is expected to carry out industrialized production.What the present invention was prepared AgCuO2It is respectively provided with certain high preferred orientation.
Description of the drawings
Fig. 1 is gained AgCuO in embodiment 12X ray diffracting spectrum, wherein, pound sign represent be base oxidation indium Diffraction maximum；
Fig. 2 is the AgCuO of gained sheet-like morphology in embodiment 12Scanning electron microscope (SEM) photograph；
Fig. 3 is gained AgCuO in embodiment 12Current density-potential figure.
Specific embodiment
The present invention is further elaborated and is illustrated with reference to the accompanying drawings and detailed description.Each enforcement in the present invention The technical characteristic of mode can carry out respective combination on the premise of not colliding with each other,.
Embodiment 1
1) working electrode, the i.e. activation of ITO electro-conductive glass：ITO electro-conductive glass 3 times is cleaned with acetone, then deionized water will be led Electric glass is placed in ultrasonic cleaner and cleans 30min, then electro-conductive glass is placed in dilute nitric acid solution and activates 30s, finally Deionized water is cleaned, standby；
2)AgCuO2The preparation of membrane electrode：By the AgNO of 0.000375mol3With the Cu (NO of 0.0003mol3)2·3H2O is in one Stirring and dissolving in quantitative distilled water, is added dropwise over the NH of 0.05mol in stirring3, it is allowed to and Ag+And Cu2+Fully it is complexed to solution Shape is clarified in navy blue, adds 0.025mol NaOH solutions to adjust the pH of solution afterwards, finally added distilled water and obtain volume and be The clarification electrolyte of 100mL；With ITO electro-conductive glass as working electrode, platinum plate electrode is that, to electrode, silver-silver chloride electrode is ginseng Than electrode, being placed in electrolyte carries out galvanostatic deposition, tests 40 DEG C of bath temperature, and it is 0.1A to apply anode constant current, is deposited Time is 1000s, and electro-deposition gained sample deionized water is dried, obtained based on the black of ITO electro-conductive glass naturally after rinsing AgCuO2Film, it is standby；
3) by step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out X-ray powder diffraction, field and sends out ESEM sign is penetrated, the data of the gained from X-ray powder diffraction instrument XRD is done into Origin8 softwares, such as Fig. 1 institutes Show, sample is (- 202) preferred orientation；Scheme the picture of the gained from field emission scanning electron microscope as SEM, as shown in Fig. 2 institute Obtain AgCuO2In rectangular body plate shape microscopic appearance；
4) by step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out respectively linear voltammetric scan, leads to Cross analysis reduction peak position, area and its corresponding specific capacity to reflect AgCuO2The discharge performance of membrane electrode；Discharge performance Test experiments are carried out in threeway electrolytic cell, electrolyte be 7M KOH solutions, electrochemical workstation model CHI660D, voltage Sweep speed is 0.1mV/s, and experiment the data obtained makees Current density-voltage figure with Origin8 softwares, as shown in figure 3, by meter Calculate the area of reduction peak, the AgCuO2Film has preferable discharge performance.
Embodiment 2
1) working electrode, the i.e. activation of ITO electro-conductive glass：ITO electro-conductive glass 3 times is cleaned with acetone, then deionized water will be led Electric glass is placed in ultrasonic cleaner and cleans 30min, then electro-conductive glass is placed in dilute nitric acid solution and activates 30s, finally Deionized water is cleaned, standby；
2)AgCuO2The preparation of membrane electrode：By the AgNO of 0.000375mol3With the Cu (NO of 0.0003mol3)2·3H2O is in one Stirring and dissolving in quantitative distilled water, is added dropwise over the NH of 0.05mol in stirring3, it is allowed to and Ag+And Cu2+Fully it is complexed to solution Shape is clarified in navy blue, adds 0.025mol NaOH solutions to adjust the pH of solution afterwards, finally added distilled water and obtain volume and be The clarification electrolyte of 100mL；With ITO electro-conductive glass as working electrode, platinum plate electrode is that, to electrode, silver-silver chloride electrode is ginseng Than electrode, being placed in electrolyte carries out galvanostatic deposition, tests 40 DEG C of bath temperature, and it is 0.1A to apply anode constant current, is deposited Time is 2000s, and electro-deposition gained sample deionized water is dried, obtained based on the black of ITO electro-conductive glass naturally after rinsing AgCuO2Film, it is standby；
3) by step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out X-ray powder diffraction, field and sends out ESEM sign is penetrated, the data of the gained from X-ray powder diffraction instrument are done into XRD with Origin8 softwares, will be sent out from field The picture for penetrating gained on ESEM is schemed as SEM, and this example gained XRD, SEM scheme the basic phase with the gained sample of embodiment 1 Together；
By step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out respectively linear voltammetric scan, passes through Analysis-reduction peak position, area and its corresponding specific capacity are reflecting AgCuO2The discharge performance of membrane electrode；Discharge performance is surveyed Examination experiment is carried out in threeway electrolytic cell, and electrolyte is 7M KOH solutions, and electrochemical workstation model CHI660D, voltage is swept It is 0.1mV/s to retouch speed, and experiment the data obtained makees Current density-voltage figure with Origin8 softwares, as a result basic with embodiment 1 It is identical.
Embodiment 3
1) working electrode, the i.e. activation of ITO electro-conductive glass：ITO electro-conductive glass 3 times is cleaned with acetone, then deionized water will be led Electric glass is placed in ultrasonic cleaner and cleans 30min, then electro-conductive glass is placed in dilute nitric acid solution and activates 30s, finally Deionized water is cleaned, standby；
2)AgCuO2The preparation of membrane electrode：By the AgNO of 0.000375mol3With the Cu (NO of 0.0003mol3)2·3H2O is in one Stirring and dissolving in quantitative distilled water, is added dropwise over the NH of 0.05mol in stirring3, it is allowed to and Ag+And Cu2+Fully it is complexed to solution Shape is clarified in navy blue, adds 0.025mol NaOH solutions to adjust the pH of solution afterwards, finally added distilled water and obtain volume and be The clarification electrolyte of 100mL；With ITO electro-conductive glass as working electrode, platinum plate electrode is that, to electrode, silver-silver chloride electrode is ginseng Than electrode, being placed in electrolyte carries out galvanostatic deposition, tests 40 DEG C of bath temperature, and it is 0.1A to apply anode constant current, is deposited Time is 3000s, and electro-deposition gained sample deionized water is dried, obtained based on the black of ITO electro-conductive glass naturally after rinsing AgCuO2Film, it is standby；
3) by step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out X-ray powder diffraction, field and sends out ESEM sign is penetrated, the data of the gained from X-ray powder diffraction instrument are done into XRD with Origin8 softwares, will be sent out from field The picture for penetrating gained on ESEM is schemed as SEM, and this example gained XRD, SEM figures are essentially identical with the gained sample of embodiment 1；
By step 2) black AgCuO of the gained based on ITO electro-conductive glass2Film carries out respectively linear voltammetric scan, passes through Analysis-reduction peak position, area and its corresponding specific capacity are reflecting AgCuO2The discharge performance of membrane electrode；Discharge performance is surveyed Examination experiment is carried out in threeway electrolytic cell, and electrolyte is 7M KOH solutions, and electrochemical workstation model CHI660D, voltage is swept It is 0.1mV/s to retouch speed, and experiment the data obtained makees Current density-voltage figure with Origin8 softwares, as a result basic with embodiment 1 It is identical.
Embodiment described above is one kind preferably scheme of the present invention, and so it is not intended to limiting the invention.Have The those of ordinary skill for closing technical field, without departing from the spirit and scope of the present invention, can also make various changes Change and modification.Such as in AgCuO2During the preparation of membrane electrode, the consumption of each reagent, can be with this not necessarily by the numerical value in embodiment Numerical value is extended in proportion.Therefore the technical scheme that all modes for taking equivalent or equivalent transformation are obtained, all falls within In protection scope of the present invention.

Claims (2)

1. one kind prepares cathode material AgCuO by anodic oxidation electro-deposition2Method, it is characterised in that it the step of it is as follows：
1) working electrode, the i.e. activation of ITO electro-conductive glass：ITO electro-conductive glass 3～5 times is cleaned with acetone, then deionized water will Electro-conductive glass is placed on 30～60min of cleaning in ultrasonic cleaner, then electro-conductive glass is placed in dilute nitric acid solution and activates 30 ～60s, last deionized water cleaning is standby；
2)AgCuO2The preparation of membrane electrode：By the AgNO of 0.000375mol3With the Cu (NO of 0.0003mol3)2·3H2O is in one Stirring and dissolving in quantitative distilled water, is added dropwise over the NH of 0.05mol in stirring3, it is allowed to and Ag+And Cu2+Fully it is complexed to solution Shape is clarified in navy blue, adds 0.025mol NaOH solutions to adjust the pH of solution afterwards, finally added distilled water and obtain volume and be The clarification electrolyte of 100mL；With ITO electro-conductive glass as working electrode, platinum plate electrode is that, to electrode, silver-silver chloride electrode is ginseng Than electrode, being placed in electrolyte carries out galvanostatic deposition, and electro-deposition gained sample deionized water is dried naturally after rinsing, and is obtained Black AgCuO based on ITO electro-conductive glass2Film.
2. the method for claim 1, it is characterised in that 40 DEG C of bath temperature is tested during galvanostatic deposition, applies anode Constant current is 0.1A, and sedimentation time is 1000～3000s.
CN201611049774.9A 2016-11-22 2016-11-22 One kind prepares cathode material AgCuO by anodic oxidation electro-deposition2Method Expired - Fee Related CN106637332B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110241433A (en) * 2019-06-24 2019-09-17 上海工程技术大学 The controllable AgCuO of size2Nano material and its preparation and application
CN110571286A (en) * 2019-08-12 2019-12-13 浙江大学 Preparation method of up-conversion rare earth fluoride and copper oxide composite electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110241433A (en) * 2019-06-24 2019-09-17 上海工程技术大学 The controllable AgCuO of size2Nano material and its preparation and application
CN110241433B (en) * 2019-06-24 2020-11-20 上海工程技术大学 Size-controllable AgCuO2 nano material and preparation and application thereof
CN110571286A (en) * 2019-08-12 2019-12-13 浙江大学 Preparation method of up-conversion rare earth fluoride and copper oxide composite electrode
CN110571286B (en) * 2019-08-12 2021-04-30 浙江大学 Preparation method of up-conversion rare earth fluoride and copper oxide composite electrode

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