CN110344097A - A method of preparing anodic titanium nano flower electrode - Google Patents
A method of preparing anodic titanium nano flower electrode Download PDFInfo
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- CN110344097A CN110344097A CN201910681587.XA CN201910681587A CN110344097A CN 110344097 A CN110344097 A CN 110344097A CN 201910681587 A CN201910681587 A CN 201910681587A CN 110344097 A CN110344097 A CN 110344097A
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- anodic
- titanium
- nano flower
- anodic titanium
- phosphoric acid
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
The invention discloses a kind of methods for preparing anodic titanium nano flower electrode.This method passes through anodizing first, prepares one layer of anodic titanium dioxide nanotube array film in titanium-based bottom surface, is then immersed in progress long-time soak at room temperature in phosphate aqueous solution, anodic titanium nano flower electrode can be obtained.Anodic titanium nano flower prepared by the present invention is by average thickness about 10~20nm, the nanometer petal of width about 250nm~1 μm is constituted, preparation method of the invention avoids use and the high-temperature process of the non-environmental protections reagent such as heavy metal ion, butyl titanate and organic solvent, and, energy conservation and environmental protection more simple and easy to do than existing method, low in cost, controllability is strong.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to a kind of method for preparing anodic titanium nano flower electrode.
Background technique
Titanium dioxide as a kind of semiconductor material, be widely used in because of its unique physical and chemical performance solar battery,
The fields such as supercapacitor, electro-catalysis and water decomposition.In recent years, as a kind of promising electrode material for super capacitor and
It receives significant attention, and its pattern, size and microstructure have an important influence on its super capacitor performance.Prepare nanometer
The titanium dioxide electrodes material of structure is the effective way for improving its energy density and power density, for this purpose, being developed each
The method that kind prepares nanometer titania, has obtained: the nano junctions such as nanotube, nano wire, nanometer sheet and nano flower
The titanium dioxide electrodes material of structure.Wherein, the titanium dioxide of nanometer flower structure have higher spacial ordering, high-specific surface area and
The characteristics such as the geometry more open compared with nano tube structure are more advantageous to load of the active material on its surface and adsorb, are a kind of
Very promising electrode microstructure.
Currently, most methods for preparing nanometer structure titanium dioxide are comparatively laborious.Such as: document [M.Ye, et
Al.Small, 9 (2012) 312-321] it reports under the auxiliary of heavy metal ion (barium, strontium, copper etc.), with tetraisopropyl titanate
For titanium source, the TiO being layered by hydro-thermal process 9h at 140 DEG C of high temperature2Nanometer flower structure.Document [X.Bai, et
Al.J.Electrochem.Soc., 165 (2018) D663-D669] by the mixed solution containing butyl titanate and hydrofluoric acid
In, at a high temperature of 200 DEG C, the TiO for being prepared for three-dimensional nanostructure is centrifuged again after carrying out hydro-thermal reaction for 24 hours2
Particle.104787800 A of Chinese patent CN, which is disclosed, places the mixed transparent solution of butyl titanate, octanol and hydrofluoric acid
In water heating kettle, it is centrifuged after being then heat-treated 3~20h at 120~200 DEG C, obtains the flower ball-shaped of different-grain diameter
TiO2The method of powder.The titanium oxide nanoflower of these documents and patent report is required to containing heavy metal ion, metatitanic acid four
It is obtained in the solution such as butyl ester and organic solvent by the methods of high temperature, prolonged hydro-thermal, solvent heat or microemulsion.Heavy metal from
The use of son will cause water pollution, be unfavorable for environmental protection；Butyl titanate facile hydrolysis, preparation process are harsh to environmental requirement；It is pungent
The organic solvents such as alcohol are also unfavorable for environmental protection；These methods are required to carry out long-time heating, cost at a high temperature of being higher than 100 DEG C
It is higher；The TiO being prepared2Nano flower is mostly powder or particle shape, cannot directly as supercapacitor or other
The electrode of device uses.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for preparing anodic titanium nano flower electrode.
The technical solution for realizing the aim of the invention is as follows: a method of anodic titanium nano flower electrode being prepared, i.e.,
First by anodizing, one layer of anodic titanium dioxide nanotube array film is prepared in titanium-based bottom surface；Then 8 are placed it in~
In the phosphate aqueous solution of 12wt%, carry out soak at room temperature 2~15 days.After take out, be washed with deionized water, dry
Obtain anodic titanium nano flower electrode.
In above-mentioned steps, when preparing anodic titanium dioxide nanotube array film, the electrolyte used is ammonium fluoride containing 0.5wt%
With the ethylene glycol solution of 2vol% water.Electrolyte temperature remains at 20 DEG C.
In above-mentioned steps, when preparing anodic titanium dioxide nanotube array film, to polish titanium foil as anode, graphite plate is yin
Pole, with current density 10mA cm-2Constant current anodic oxidation, or with 60V constant pressure anodic oxidation 5min.
Compared with prior art, the present invention has remarkable advantage are as follows: 1, this method step is easy, low in cost, energy-saving ring
The anodic titanium nano flower protect, obtained can be used directly as device electrode；2, the present invention can be by changing phosphoric acid dip item
Part (concentration and time) is realized to anodic titanium nano flower pattern；3, anodic titanium nanometer flower prepared by the present invention
Structure is special, more open relative to existing anodic titanium nano tube structure, is conducive to other active materials in its adsorption.
Detailed description of the invention
Fig. 1 is the SEM figure for the sample surface morphology that embodiment 1 obtains.
Fig. 2 is the SEM figure for the sample surface morphology that comparative example 1 obtains.
Specific embodiment
In order to be best understood from the present invention, the present invention is further illustrated below by embodiment.
Embodiment 1
The titanium foil sheet that the thickness that purity is 99.5%, 6cm × 1cm is 100 μm is immersed into polishing fluid HF:HNO first3:H2O body
15s is handled in the mixed liquor that product ratio is 1:1:2, to remove the oxidation film on titanium foil surface.Then it is cleaned with deionized water, finally certainly
It so dries spare.Using this titanium foil sheet as anode, using graphite flake as cathode, containing 0.5wt%NH4F and 2vol%H2The ethylene glycol of O
Anodic oxidation is carried out in electrolyte.With current density 10mA cm-2Constant current anodic oxidation, or with 60V constant pressure anodic oxidation 5min.
Electrolyte temperature remains at 20 DEG C or so.It after anodic oxidation, is cleaned with deionized water, naturally dry is spare.
Titanium foil sheet after anodic oxidation is placed in 10wt% phosphate aqueous solution, soak at room temperature is handled 4 days.After take out
Titanium foil sheet is washed with deionized water, dries.The anodic titanium nano flower of preparation is by the petal structure of width about 880nm
At.Pattern is as shown in Figure 1, titanium oxide nanoflower is that dissolving-recrystallization occurs under the action of phosphoric acid by titania nanotube
What oriented growth obtained.
Embodiment 2
Specification, pretreatment and the anode oxidation process of titanium foil sheet are with embodiment 1, and change phosphoric acid concentration is 8wt%, often
Warm immersion treatment 15 days.The anodic titanium nano flower of preparation is made of about 1 μm of width of petal.
Embodiment 3
For specification, pretreatment and the anode oxidation process of titanium foil sheet with embodiment 1, change phosphoric acid concentration is 12wt%,
Soak at room temperature is handled 2 days.The anodic titanium nano flower of preparation is made of the petal of width about 650nm.
Embodiment 4
For specification, pretreatment and the anode oxidation process of titanium foil sheet with embodiment 1, change phosphoric acid concentration is 15wt%,
The immersion treatment time is the same as embodiment 1.It, can not by the complete corrosion dissolution of the titanium dioxide on titanium foil surface since phosphoric acid concentration is too big
Obtain anodic titanium nano flower electrode.
Embodiment 5
With embodiment 1, change the soak at room temperature processing time is specification, pretreatment and the anode oxidation process of titanium foil sheet
5 days, phosphoric acid concentration was the same as embodiment 1.The anodic titanium nano flower of preparation is made of the petal of width about 960nm.
Embodiment 6
With embodiment 1, change the soak at room temperature processing time is specification, pretreatment and the anode oxidation process of titanium foil sheet
2 days, phosphoric acid concentration was the same as embodiment 1.The anodic titanium nano flower of preparation is made of the petal of width about 250nm.
Embodiment 7
With embodiment 1, change the soak at room temperature processing time is specification, pretreatment and the anode oxidation process of titanium foil sheet
3 days, phosphoric acid concentration 12wt%.The anodic titanium nano flower of preparation is made of the petal of width about 900nm.
Embodiment 8
With embodiment 1, change the soak at room temperature processing time is specification, pretreatment and the anode oxidation process of titanium foil sheet
5 days, phosphoric acid concentration 9wt%.The anodic titanium nano flower of preparation is made of the petal of width about 850nm.
Embodiment 9
Commercially available titania powder is subjected to soak at room temperature processing, phosphoric acid concentration and immersion treatment technique with embodiment 1,
It since commercially available titania powder is crystal, is handled by phosphoric acid dip, dissolve-repreparation process can not be carried out, through SEM table
It levys and is now unable to get titanium oxide nanoflower electrode.
Comparative example 1
With embodiment 1, change the soak at room temperature processing time is specification, pretreatment and the anode oxidation process of titanium foil sheet
12h.The sample surfaces of preparation are nanometer grass pattern, as shown in Fig. 2, nano titania grass is titanium dioxide under the action of phosphoric acid
It is lysigenous that part occurs for titanium nanotube.
It, only need to be by the anodic titanium dioxide nanotube array film prepared in phosphoric acid solution using method of the present invention
The soak at room temperature sufficiently long time, anodic titanium nano flower can be obtained.This is because the titanium oxide of anodizing preparation
Nanotube is non crystalline structure, and dissolve-repreparation process can occur for titanium oxide under the action of soaking of phosphoric acid.In this process,
Anodic titanium nanotube changes pattern because of crystallization, and oxidation titanium crystal is grown along nanotube orientation preferentially, ultimately forms nanometer
Floral structure.This is the process of spontaneous progress under a room temperature, without energy consumption.Prepared nanometer flower structure is more compared to nanotube
It is open, be conducive to other active materials in the load on its surface, titanium dioxide electrodes material is made more preferably to meet the neck such as energy storage device
The application requirement in domain.
Claims (6)
1. a kind of method for preparing anodic titanium nano flower electrode, which is characterized in that by anodizing, in titanium substrate table
Wheat flour is for one layer of anodic titanium dioxide nanotube array film；Then place it in phosphate aqueous solution carry out soak at room temperature, after take
It is washed with deionized water, dries out, anodic titanium nano flower electrode can be obtained.
2. the method as described in claim 1, which is characterized in that when preparation anodic titanium dioxide nanotube array film, anodic oxidation
The electrolyte used in method remains at for the ethylene glycol solution of ammonium fluoride containing 0.5wt% and 2vol% water, electrolyte temperature
20℃。
3. the method as described in claim 1, which is characterized in that when preparation anodic titanium dioxide nanotube array film, with polishing titanium
Foil is anode, and graphite plate is cathode, with current density 10mA cm-2Constant current anodic oxidation, or with 60V constant pressure anodic oxidation 5min.
4. the method as described in claim 1, which is characterized in that the concentration of phosphate aqueous solution used in phosphoric acid dip process is
8~12wt%.
5. the method as described in claim 1, which is characterized in that the time of phosphoric acid dip processing is 2~15 days.
6. method as claimed in claim 5, which is characterized in that the time of phosphoric acid dip processing is 4 days.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030177A (en) * | 2012-12-25 | 2013-04-10 | 王滨 | Preparation method of titanium oxide nanoflower film |
| CN103165283A (en) * | 2013-03-22 | 2013-06-19 | 南京理工大学 | Method for enhancing electrochemical performance of TiO2 electrode |
| CN105727998A (en) * | 2016-02-01 | 2016-07-06 | 浙江工商大学 | Composite titanium dioxide nanoflower photoelectrocatalysis material and preparation and application thereof |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
| CN110033960A (en) * | 2019-04-22 | 2019-07-19 | 南京理工大学 | A method of preparing titanium oxide nanoflower electrode |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030177A (en) * | 2012-12-25 | 2013-04-10 | 王滨 | Preparation method of titanium oxide nanoflower film |
| CN103165283A (en) * | 2013-03-22 | 2013-06-19 | 南京理工大学 | Method for enhancing electrochemical performance of TiO2 electrode |
| CN105727998A (en) * | 2016-02-01 | 2016-07-06 | 浙江工商大学 | Composite titanium dioxide nanoflower photoelectrocatalysis material and preparation and application thereof |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
| CN110033960A (en) * | 2019-04-22 | 2019-07-19 | 南京理工大学 | A method of preparing titanium oxide nanoflower electrode |
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