CN108807004A - A kind of NiO/H-TiO2The preparation method of nanometer tube combination electrode - Google Patents

A kind of NiO/H-TiO2The preparation method of nanometer tube combination electrode Download PDF

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Publication number
CN108807004A
CN108807004A CN201810659799.3A CN201810659799A CN108807004A CN 108807004 A CN108807004 A CN 108807004A CN 201810659799 A CN201810659799 A CN 201810659799A CN 108807004 A CN108807004 A CN 108807004A
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electrode
tio
nanotube
nio
preparation
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Inventor
李刚
郭丽芳
李廷鱼
段淑斐
王开鹰
孙雅静
赵清华
李朋伟
胡杰
张文栋
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Taiyuan University of Technology
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Taiyuan University of Technology
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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
    • 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
    • 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
    • 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 one kind being based on TiO2Method prepared by nanotube electrochemical modification and its combination electrode, specially anodizing, electrochemical reducing and differential pulse method, which are combined, prepares TiO2Nano-tube array, then be modified, deposition of electrode material is to prepare high-performance combination electrode.Its technical solution is：First using pure titanium as substrate in two electrode systems, structurally ordered, morphology controllable, pipe range and the controllable Nano tube array of titanium dioxide of thickness are prepared using an anodizing；Secondly in two electrode systems, reversely powering up pressure processing carries out electrochemistry hydrogen loading；Finally by the H-TiO of preparation2Nanotube carries out electrochemical deposition nickel oxide nanoparticle in three-electrode system by differential pulse voltammetry.NiO/H-TiO prepared by this method2Combination electrode nano particle is evenly distributed, and size tunable, electric conductivity is strong, has higher specific capacitance and energy density, can more preferably be applied to electrochemical energy storage field and area of solar cell.

Description

A kind of NiO/H-TiO2The preparation method of nanometer tube combination electrode
Technical field
The invention belongs to energy storage technologies field, specially a kind of NiO/H-TiO2The preparation side of nanometer tube combination electrode Method, this method prepare NiO/H-TiO using the method that anodizing, electrochemical reducing and differential pulse method are combined2 Nanometer tube combination electrode, the NiO/H-TiO prepared by this method2Nanometer tube combination electrode has preferable electric conductivity and superelevation Energy density, for improve energy storage device performance provide new thinking.
Background technology
In recent years, due to ultracapacitor power density is big, charge/discharge rates are fast, cycle lie is long, cyclical stability is strong, The advantages such as cleanliness without any pollution obtain the general of people in electronic product, solar cell, distributed energy storage and new-energy automobile field All over concern.Ultracapacitor can be divided into double layer capacitor and fake capacitance capacitor by reaction mechanism.Electric double layer capacitance utensil There are the advantages such as the fast, long lifespan of charge/discharge rates, but the energy density of double layer capacitor is relatively low and electric conductivity is poor, limits it Application field.Fake capacitance capacitor redox reaction is happened at active electrode surface, has high specific capacitance and high-energy density, Its specific capacitance is 4-10 times of electric double layer capacitance.So far, ruthenium oxide hydration is that most have in various fake capacitance electrode materials The electrode material of future, however the high cost of ruthenium-oxide limits its application in ultracapacitor.
Due to TiO2Nanotube has lower-cost preparation process, big specific surface area, good electron-transport path, There is potential application value in ultracapacitor field.But due to original TiO2The semiconductor properties of nanotube, electric conductivity is very poor, Lower electric double layer capacitance is showed, it cannot be directly as electrode material.Experimental results demonstrate to TiO2Nanotube is doped It is a kind of effective modified method.Currently, effective TiO the most economical and simple2Nanotube doping method is electrochemical reduction Method.However, it is simple by electrochemical reduction method to TiO2Nanotube carries out auto-dope, to a certain extent to its capacitance Performance increases, but reaches use demand far away.Therefore, the TiO with high electrical conductivity2Nanotube is more suitable for super The fake capacitance electrode material of the skeleton structure deposited capacitances better performances of capacitor, to increase substantially capacitor performance, more It is applied to electrochemical energy storage field and area of solar cell well.
Invention content
In view of the above existing problems in the prior art, the present invention provides a kind of electrochemical doping TiO2Nanotube is as skeleton Material deposits the method that fake capacitance electrode material NiO forms combination electrode.TiO prepared by this method2Nanometer tube combination electrode has There are Fabrication of High Specific Capacitance, high conductivity and high-energy density, the dielectric capacitor with super capacitor energy density magnitude can be prepared.
To achieve the goals above, the technical solution adopted by the present invention is：A kind of NiO/H-TiO2Nanometer tube combination electrode Preparation method, using a variety of electrochemical process to TiO2Electrode is modified, and its step are as follows：
1) in two electrode systems, the controllable TiO of three-dimensional appearance is prepared2Nanotube, and clean, drying and calcination；2) two In electrode system, to TiO2Nanotube electrode adds backward voltage processing to introduce hydrogen doping, and H-TiO is made2Nanotube；
3) to H-TiO obtained2Nanotube electrode carries out the hydroxide of electrochemical deposition nickel in three-electrode system, through forging It burns, obtains NiO/H-TiO2Nanotube electrode.
A kind of above-mentioned NiO/H-TiO2The preparation method of nanometer tube combination electrode prepares the controllable TiO of three-dimensional appearance2It receives Using titanium sheet as anode when mitron, graphite is used as to electrode, by titanium sheet respectively in acetone, ethyl alcohol and deionization before anodic oxidation It is cleaned by ultrasonic in water 10 minutes, is then 0.25%NH in the mass ratio configured4The electrolysis of the ethylene glycol of F and 2% deionized water Anodic oxidation is carried out in liquid, and the titanium sheet after anodic oxidation is cleaned, is dried.
A kind of above-mentioned NiO/H-TiO2The preparation method of nanometer tube combination electrode, the controllable TiO of the three-dimensional appearance of preparation2 The length range of nanotube is 12-15 μm, caliber ranging from 107-128nm, and external diametrical extent is 170-500 nm.
A kind of above-mentioned NiO/H-TiO2The preparation method of nanometer tube combination electrode, TiO2The calcination temperature of nanotube exists 400-600℃。
A kind of above-mentioned NiO/H-TiO2The preparation method of nanometer tube combination electrode, with TiO2Nano-tube array is cathode, stone Ink is anode, in 0.5M Na2SO4Electrochemistry hydrogen loading processing is carried out in electrolyte, two interelectrode distances are 2-3cm, apply voltage It is 30s for 5V and reacting treatment time.
A kind of above-mentioned NiO/H-TiO2The preparation method of nanometer tube combination electrode, with H-TiO2Nanotube electrode is work Electrode, Hg/Hg2Cl2Electrode is reference electrode, and gauze platinum electrode is to electrode, in 0.04 M NiCl2Pass through difference arteries and veins in electrolyte Voltammetry electrochemical deposition nickel is rushed, after electrochemical deposition, using cyclic voltammetry in -1 V in 1M KOH solutions1 10 pulse periods are scanned with 100 mV/s in V voltage ranges, complete metal hydroxides is formed, becomes aoxidizing after calcining Nickel.
Compared with the prior art, the advantages of the present invention are as follows by electrochemical modification twice：For the first time in two electrode systems In to TiO2Nanotube adds backward voltage hydrogen loading to handle, and method is simple；Second of the modified electrochemistry in three-electrode system The hydroxide that electrochemical deposition nickel is carried out in work station can easily show that constant current charge-discharge curve and cycle lie prostrate in the process Pacify curve.This method is admirably to TiO2Nanotube has carried out auto-dope, electric conductivity enhancing, and specific capacitance significantly increases, electrification It learns performance to be improved significantly, to there is better application prospect.
Description of the drawings
Fig. 1 is untreated TiO prepared by embodiment 12The appearance structure of nanotube.
Fig. 2 is the NiO/H-TiO of electrochemical modification prepared by embodiment 32The appearance structure of nanotube.
Fig. 3 is untreated TiO prepared by embodiment 12The Cyclic voltamogram curve of nanotube electrode.
Fig. 4 is the TiO of H doping prepared by embodiment 22The Cyclic voltamogram curve of nanotube electrode.
Fig. 5 is the NiO/H-TiO of electrochemical modification prepared by embodiment 32The Cyclic voltamogram curve of nanotube electrode.
Fig. 6 is untreated TiO prepared by embodiment 12The constant current charge-discharge characteristic curve of nanotube electrode.
Fig. 7 is the TiO of H doping prepared by embodiment 22The constant current charge-discharge characteristic curve of nanotube electrode.
Fig. 8 is the NiO/H-TiO of electrochemical modification prepared by embodiment 32The constant current charge-discharge characteristic of nanotube electrode Curve.
Specific implementation mode
Embodiment 1
The controllable TiO of three-dimensional appearance is prepared using constant-voltage method in two electrode systems2Nanotube electrode：Technical pure titanium sheet is distinguished In acetone, 10 min are cleaned by ultrasonic in absolute ethyl alcohol and deionized water, it is dry.At room temperature, using titanium sheet as anode, with stone Ink is, to electrode, titanium sheet, at a distance of 2-3cm, is 0.25%NH in the mass fraction configured with graphite electrode4F and 2% deionized water Ethylene glycol solution in apply constant voltage carry out anodic oxidation.By the TiO of generation after anodic oxidation2Nanotube electrode exists It is cleaned by ultrasonic 30s in absolute ethyl alcohol, removes the remaining electrolyte in nanotube surface layer.Obtained TiO2The length range of nanotube is 12-15 μm, caliber ranging from 107-128nm, external diametrical extent is 170-500 μm.By amorphous TiO2Nanotube electrode is put into It is calcined in tube furnace, calcination temperature is 450 DEG C.
Embodiment 2
The controllable TiO of three-dimensional appearance2Prepared by nanotube electrode and calcination temperature is with embodiment 1, with crystalline state TiO2Nano-tube array For cathode, graphite is anode in 0.5MNa2SO4Electrochemistry hydrogen loading processing is carried out in electrolyte, two interelectrode distances are 2-3cm, are applied Making alive is 5V and reacting treatment time is 30s.
Embodiment 3
The controllable TiO of three-dimensional appearance2Prepared by nanotube electrode and calcination temperature is the same as embodiment 1, the TiO of H doping2Nanotube electrode It prepares with embodiment 2, with H-TiO2Nanotube electrode is working electrode, Hg/Hg2Cl2Electrode is as reference electrode, gauze platinum electrode As to electrode, in 0.04MNiCl2The hydroxide of electrochemical deposition nickel is carried out in electrolyte by differential pulse voltammetry, After electrochemical deposition, cyclic voltammetry is used to be swept with 100 mV/s in -1 V -1 V voltage ranges in 1M KOH solutions 10 pulse periods are retouched, complete metal hydroxides is formed, become NiO/H-TiO through 300 DEG C of calcinings in tube furnace2It receives Mitron combination electrode.

Claims (6)

1. a kind of NiO/H-TiO2The preparation method of nanometer tube combination electrode, it is characterised in that use a variety of electrochemical process pair TiO2Electrode is modified, and its step are as follows：
1) in two electrode systems, the controllable TiO of three-dimensional appearance is prepared2Nanotube, and clean, drying and calcination；
2) in two electrode systems, to TiO2Nanotube electrode adds backward voltage processing to introduce hydrogen doping, and H-TiO is made2Nanotube Electrode；
3) in three-electrode system, to H-TiO made from 2)2The hydroxide of nanotube electrode electrochemical deposition nickel, through calcining, Obtain NiO/H-TiO2Nanotube electrode.
2. a kind of NiO/H-TiO as described in claim 12The preparation method of nanometer tube combination electrode, it is characterised in that prepare three Tie up the TiO of morphology controllable2Using titanium sheet as anode when nanotube, graphite is used as to electrode, and titanium sheet exists respectively before anodic oxidation It is cleaned by ultrasonic in acetone, ethyl alcohol and deionized water 10 minutes, is then 0.25%NH in mass ratio4The second of F and 2% deionized water Anodic oxidation is carried out in the electrolyte of glycol, and the titanium sheet after anodic oxidation is cleaned, is dried.
3. a kind of NiO/H-TiO as claimed in claim 1 or 22The preparation method of nanometer tube combination electrode, it is characterised in that system The controllable TiO of standby three-dimensional appearance2The length range of nanotube is 12-15 μm, caliber ranging from 107-128nm, external diametrical extent For 170-500 nm.
4. a kind of NiO/H-TiO as claimed in claim 1 or 22The preparation method of nanometer tube combination electrode, it is characterised in that TiO2The calcination temperature of nanotube is at 400-600 DEG C.
5. a kind of NiO/H-TiO as claimed in claim 1 or 22The preparation method of nanometer tube combination electrode, it is characterised in that with TiO2Nano-tube array is cathode, and graphite is anode, in 0.5M Na2SO4Electrochemistry hydrogen loading processing, two electrodes are carried out in electrolyte Between distance be 2-3cm, it is 5V and reacting treatment time is 30s to apply voltage.
6. a kind of NiO/H-TiO as claimed in claim 1 or 22The preparation method of nanometer tube combination electrode, it is characterised in that with H-TiO2Nanotube electrode is working electrode, Hg/Hg2Cl2Electrode is reference electrode, and gauze platinum electrode is to electrode, in 0.04 M NiCl2By differential pulse voltammetry electrochemical deposition nickel in electrolyte, after electrochemical deposition, adopted in 1M KOH solutions With cyclic voltammetry in -1 V10 pulse periods are scanned with 100 mV/s in 1 V voltage ranges, form complete metallic hydrogen Oxide becomes nickel oxide after calcining.
CN201810659799.3A 2018-06-25 2018-06-25 A kind of NiO/H-TiO2The preparation method of nanometer tube combination electrode Pending CN108807004A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN112981452A (en) * 2021-02-05 2021-06-18 深圳职业技术学院 Water oxidation electrocatalyst and preparation method thereof, and water oxidation electrode and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Application publication date: 20181113