CN105118694B - A kind of preparation method of Al-Doped ZnO nano-array - Google Patents
A kind of preparation method of Al-Doped ZnO nano-array Download PDFInfo
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Abstract
A kind of preparation method of Al-Doped ZnO nano-array,The preparation method is to inject growth source and doped source by continuous constant rate of speed,The concentration of accurate control chemical reaction liquid,So as to which controllable preparation goes out the Al-Doped ZnO array of high carrier concentration,And with nickel oxide material is compound obtains the capacitor electrode material of high power capacity,A kind of capacitor electrode material,The electrode material is combined gained as the high nickel oxide nano sheet material of aluminium-doped zinc oxide nano-array and the poorly conductive but capacitance of the high conductivity prepared by continuous Flow Injection Analysis,The carrier concentration of the invention compared with common hydro-thermal method improves 3 orders of magnitude,The nickel oxide of the aluminium-doped zinc oxide material of this high carrier concentration and poorly conductive is combined,Give full play to both advantages,The capacitance of capacitor can be increased substantially,Continuous flow injection doping method provides new approaches for controllable accurate doping and technique is simple,Cost is cheap,There is good application prospect.
Description
Technical field
The present invention relates to the technical field of electrode material performance, more particularly to a kind of preparation of Al-Doped ZnO nano-array
Method.
Background technology
Today's society, under the serious pressure of energy crisis and environmental pollution, the storage of the energy is particularly important.It is super
Capacitor has the advantages that energy density is high, the discharge and recharge time is short, has extended cycle life as a kind of new energy storage device
Widely studied and applied in various electronic products.The key factor for determining performance of the supercapacitor is electrode material electrification
The quality of performance is learned, therefore synthesize a kind of electrode material of function admirable to have turned into the focus of people's research.Traditional super electricity
Container electrode material can be divided into three major types, carbon material, conducting polymer materials and transistion metal compound, wherein transition gold
Category compound possesses multiple accessible valence state centers, is more easy to that reversible electrochemical reaction occurs, therefore have larger electric capacity
Amount, such as：NiO theoretical capacities can reach 2573Fg-1, but the actual capacitance of transistion metal compound but not ten sub-argument
To think, main cause is its poorly conductive, and in order to solve this problem, researcher proposes the various methods for improving its electrical conductivity,
Such as doping vario-property, pretreatment and composite modified.
Wherein composite modified is considered as a kind of maximally efficient modified method.Composite modified is by transition metal compound
A kind of method of material conductivity is improved together with the thing Material cladding high with electrical conductivity, currently used for composite modified material
Mainly have：Graphene, carbon fiber, zinc oxide and metal nanoparticle.Zinc oxide is received due to cheap and environment-friendly
Extensive favor.In addition, One-Dimensional ZnO nanometer rods are due to its unidirectional electron transmission characteristic and as the focus material of composite modified research
Material.In the recent period, some scholars also attempt to improve the electricity of transistion metal compound using the preferable Al doping zinc oxide nanometers rod of electric conductivity
Conductance.Traditional ald adulterates and magnetron sputtering doping techniques complex process, cost are high and forms polycrystal film mostly
It is not easy electric transmission.J. Liu etc.（Liu J, Xu L, Wei B, et al. One-step hydrothermal
synthesis and optical properties of aluminium doped ZnO hexagonal nanoplates
on a zinc substrate. CrystEngComm, 2011, 13:1283-1286）It is cheap using quick direct and cost
Hydrothermal reaction at low temperature successfully synthesize Al doping zinc oxide nanometer sheets, yet with the change of reactant concentration in reaction cavity, it is difficult to
The uniformity of the effective pattern and doping for ensureing reactant.
The content of the invention
In order to solve the above problems, the present invention provides a kind of preparation method of Al-Doped ZnO nano-array, the preparation
Method is to inject growth source and doped source, the accurate concentration for controlling chemical reaction liquid, so as to controllable by continuous constant rate of speed
It is standby go out high carrier concentration Al-Doped ZnO array, and with the compound electrode for capacitors material for obtaining high power capacity of nickel oxide material
Material；
Further, the preparation method comprises the following steps that：
（1）Glass is cleaned and magnetron sputtering deposition mixes Al zinc-oxide film as crystal seed layer, this substrate is brilliant
Kind layer is placed in the liquid-phase chemical reaction chamber of continuous growing device upwards；
（2）Prepare 50mM zinc nitrates and 5mM aluminum nitrates mixed aqueous solution and be injected into continuous growing device used its
In a syringe；
（3）50mM hexas are prepared to be injected into another syringe of device as alkali salt；
（4）Liquid-phase chemical reaction chamber temperature is maintained at 95 DEG C by heating water bath, sets the constant charge velocity of reaction source
(6ml/h) and constant injection length（16h）Start continuous Flow Injection Analysis preparation and mix aluminium ZnO arrays；
（5）After hydro-thermal reaction terminates, stop heating response chamber, it is to be cooled to arrive room temperature, sample is taken out, uses deionized water rinsing
And nitrogen dries up；
（6）Capacitor electrode material is constructed mixing aluminium ZnO array outer cladding NiO nanometer sheets by chemical bath deposition method；
Further, the syringe of described continuous growing device shares two, can be pushed ahead with constant speed
Growth-promoting media is injected into reaction chamber, at the same time, waste liquid caused by reaction can discharge at the same rate；
Further, the cleaning method of the glass is to be cleaned by ultrasonic respectively with acetone, isopropanol, deionized water respectively
10min, then dried up with nitrogen；
Further, the zinc oxide films film thickness that described magnetron sputtering deposition mixes Al is 500nm；
Further, it by 40ml concentration is 1M nickel sulfates that the chemical deposition, which is, 30ml concentration is 0.25M persulfuric acid
Potassium and 10ml ammoniacal liquor are added sequentially to be used as deposition solution in 100ml beakers, the aluminium doping zinc oxide nanometer rod array that will have been prepared
Sample, stand upright in above-mentioned deposition solution and carry out the deposition reaction of nickel source, after being reacted 30 minutes under 25 degrees Celsius, take out sample
Product, anneal 1.5 hours in 350 degree of air；
Further, a kind of capacitor electrode material, the electrode material is as the height electricity prepared by continuous Flow Injection Analysis
The aluminium-doped zinc oxide nano-array of conductance and poorly conductive but the high nickel oxide nano sheet material of capacitance is combined gained；
Further, the thickness of the nickel oxide nano sheet material is 100-200nm.
Beneficial effects of the present invention are as follows：
1）Using two syringes, pushed ahead with constant speed and growth-promoting media is injected into reaction chamber, waste liquid is with same
Speed is discharged, and the constant concentration of growth-promoting media in reaction chamber is controlled with this；
2）The zinc oxide films film thickness that magnetron sputtering deposition mixes Al is 500nm, and it is as mixing aluminium ZnO nano array hydro-thermal
The crystal seed layer of growth is so as to ensureing its more preferable crystallinity and chemical orientation；
3）Constant charge velocity can accurately control the ratio of growth source, doped source and alkali salt, keep constant pH value, have
Zn atoms are substituted beneficial to Al atoms, so as to synthesize uniform aluminium doping zinc oxide nanometer rod array;
4）By the aluminium-doped zinc oxide nano-array of the high conductivity prepared by continuous Flow Injection Analysis and poorly conductive but
The high nickel oxide nano sheet material of capacitance combines, and can give full play to both advantages, increase substantially electrode of super capacitor material
The capacitance of material；
5）Al-Doped ZnO material prepared by the present invention carrier concentration compared with common hydro-thermal method improves 3 quantity
Level.The nickel oxide of the aluminium-doped zinc oxide material of this high carrier concentration and poorly conductive is combined, gives full play to two
Person's advantage, the capacitance of capacitor can be increased substantially；
6）This continuous flow injection doping method provides new approaches for controllable accurate doping and technique is simple, and cost is low
It is honest and clean, there is good application prospect.
Brief description of the drawings
Fig. 1 is continuous flowing injection device figure；
Fig. 2 is continuous growth Al-Doped ZnO array scanning electron microscope；
Fig. 3 is continuous growth Al-Doped ZnO array scanning energy spectrum diagram；
Fig. 4 is conventional hydrothermal method Al-Doped ZnO array carrier concentration figure；
Fig. 5 is continuous growth Al-Doped ZnO array carrier concentration figure；
Fig. 6 is conventional hydrothermal method Al-Doped ZnO array and continuous growth Al-Doped ZnO Array Cycle volt-ampere curve and perseverance
Flow charging and discharging curve comparison diagram；
Fig. 7 is that embodiment 1 continuously grows Al-Doped ZnO array scanning electron microscope；
Fig. 8 is that embodiment 2 continuously grows Al-Doped ZnO array scanning electron microscope；
Fig. 9 is that embodiment 3 continuously grows Al-Doped ZnO array scanning electron microscope.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.On the contrary, the present invention cover it is any be defined by the claims the present invention spirit and scope on do
Replacement, modification, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to this
It is detailed to describe some specific detail sections in the detailed description of invention.It is thin without these for a person skilled in the art
The description of section part can also understand the present invention completely.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but not as a limitation of the invention.
Below most preferred embodiment is enumerated for the present invention：
A kind of preparation method of Al-Doped ZnO nano-array, the preparation method are to inject to give birth to by continuous constant rate of speed
Long source and doped source, the accurate concentration for controlling chemical reaction liquid, so as to which controllable preparation goes out the Al-Doped ZnO of high carrier concentration
Array, and with nickel oxide material is compound obtains the capacitor electrode material of high power capacity, the preparation method comprises the following steps that：
（1）Glass is cleaned and magnetron sputtering deposition mixes Al zinc-oxide film as crystal seed layer, this substrate is brilliant
Kind layer is placed in the liquid-phase chemical reaction chamber of continuous growing device upwards；
（2）Prepare 50mM zinc nitrates 5mM aluminum nitrates mixed aqueous solution and be injected into continuous growing device used wherein
A syringe；
（3）50mM hexas are prepared to be injected into another syringe of device as alkali salt；
（4）Liquid-phase chemical reaction chamber temperature is maintained at 95 DEG C by heating water bath, sets the constant charge velocity of reaction source
(6ml/h) and constant injection length（16h）Start continuous Flow Injection Analysis preparation and mix aluminium ZnO arrays；
（5）After hydro-thermal reaction terminates, stop heating response chamber, it is to be cooled to arrive room temperature, sample is taken out, uses deionized water rinsing
And nitrogen dries up；
（6）Capacitor electrode material is constructed mixing aluminium ZnO array outer cladding NiO nanometer sheets by chemical bath deposition method.
The syringe of described continuous growing device shares two, can be pushed ahead with constant speed and note growth-promoting media
Enter reaction chamber, at the same time, waste liquid caused by reaction can discharge at the same rate, and the cleaning method of the glass is to use respectively
Acetone, isopropanol, deionized water are cleaned by ultrasonic 10min respectively, are then dried up with nitrogen, and the chemical deposition is by 40ml
Concentration is 1M nickel sulfates, 30ml concentration is that 0.25M potassium peroxydisulfates and 10ml ammoniacal liquor are added sequentially to make in 100ml beakers
For deposition solution, the aluminium doping zinc oxide nanometer rod array sample that will have been prepared, stand upright on and nickel source is carried out in above-mentioned deposition solution
Deposition reaction, after reacting 30 minutes under 25 degrees Celsius, take out sample, annealed 1.5 hours in 350 degree of air, described magnetic control
The zinc oxide films film thickness that sputtering sedimentation mixes Al is 500nm.
A kind of capacitor electrode material, the electrode material are mixed as the aluminium of the high conductivity prepared by continuous Flow Injection Analysis
Miscellaneous zinc oxide nano array and poorly conductive but the high nickel oxide nano sheet material of capacitance is combined gained, the nickel oxide nano
The thickness of sheet material is 100-200nm.
Embodiment 1：
（1）Glass is cleaned and magnetron sputtering deposition mixes Al zinc-oxide film as crystal seed layer, this substrate is brilliant
Kind layer is placed in the liquid-phase chemical reaction chamber of continuous growing device upwards；
（2）Prepare 50mM zinc nitrates and 5mM aluminum nitrates mixed aqueous solution and be injected into continuous growing device used
One of syringe；
（3）50mM hexas are prepared to be injected into another syringe of device as alkali salt；
（4）Liquid-phase chemical reaction chamber temperature is maintained at 95 DEG C by heating water bath, sets the constant charge velocity of reaction source
(6ml/h) and constant injection length（16h）Start continuous Flow Injection Analysis preparation and mix aluminium ZnO arrays；
（5）After hydro-thermal reaction terminates, stop heating response chamber, it is to be cooled to arrive room temperature, sample is taken out, uses deionized water rinsing
And nitrogen dries up；
（6）Be 1M nickel sulfates by 40ml concentration, 30ml concentration be that 0.25M potassium peroxydisulfates and 10ml ammoniacal liquor sequentially add
Deposition solution is used as into 100ml beakers.The aluminium doping zinc oxide nanometer rod array sample that will have been synthesized, stands upright on above-mentioned deposition
The deposition reaction of nickel source is carried out in solution.After being reacted 30 minutes under 25 degrees Celsius, sample is taken out, annealing 1.5 is small in 350 degree of air
When obtain electrode material for super capacitor.
Embodiment 2：
Other steps such as embodiment 1 is constant, will not be repeated here, simply step（3）It is changed to：The methylenes of 50mM six are prepared respectively
Urotropine and 5M sodium hydroxide solutions keep the addition of hexa constant, by changing sodium hydroxide as alkali lye
Addition alkali lye PH is adjusted to be injected into after 5.00 in another syringe of device.
Embodiment 3：
Other steps such as embodiment 1 is constant, will not be repeated here, simply step（3）It is changed to：The methylenes of 50mM six are prepared respectively
Urotropine and 5M sodium hydroxide solutions keep the addition of hexa constant, by changing sodium hydroxide as alkali lye
Addition alkali lye PH is adjusted to be injected into after 6.00 in another syringe of device.
One kind of embodiment described above, simply more preferably embodiment of the invention, those skilled in the art
The usual variations and alternatives that member is carried out in the range of technical solution of the present invention should all include within the scope of the present invention.
Claims (7)
1. a kind of preparation method of Al-Doped ZnO nano-array, it is characterised in that the preparation method is by continuous constant
Speed injects growth source and doped source, the accurate concentration for controlling chemical reaction liquid, so as to which controllable preparation goes out high carrier concentration
Al-Doped ZnO array, and with nickel oxide material is compound obtains the capacitor electrode material of high power capacity, the preparation method is specific
Step is as follows：
(1) glass is cleaned and magnetron sputtering deposition mixes Al zinc-oxide film as crystal seed layer, by this substrate crystal seed layer
It is placed in upwards in the liquid-phase chemical reaction chamber of continuous growing device；
(2) 50mM zinc nitrates and 5mM aluminum nitrates mixed aqueous solution are prepared and to be injected into continuous growing device used therein
One syringe；
(3) 50mM hexas are prepared to be injected into another syringe of device as alkali salt；
(4) liquid-phase chemical reaction chamber temperature is maintained at 95 DEG C by heating water bath, set the constant charge velocity of reaction source as
6ml/h and constant injection length are 16h, start continuous Flow Injection Analysis preparation and mix aluminium ZnO arrays；
(5) after hydro-thermal reaction terminates, heating response chamber is stopped, it is to be cooled to arrive room temperature, sample is taken out, with deionized water rinsing and nitrogen
Air-blowing is done；
(6) capacitor electrode material is constructed mixing aluminium ZnO array outer cladding NiO nanometer sheets by chemical bath deposition method.
2. preparation method according to claim 1, it is characterised in that the syringe of described continuous growing device shares two
It is individual, it can be pushed ahead with constant speed and growth-promoting media is injected into reaction chamber, at the same time, waste liquid caused by reaction can be with same
Speed discharge.
3. preparation method according to claim 1, it is characterised in that the cleaning method of the glass for respectively with acetone,
Isopropanol, deionized water are cleaned by ultrasonic 10min respectively, are then dried up with nitrogen.
4. preparation method according to claim 1, it is characterised in that described magnetron sputtering deposition mixes Al zinc oxide films
Film thickness is 500nm.
5. preparation method according to claim 1, it is characterised in that it by 40ml concentration is 1M that the chemical bath deposition method, which is,
Nickel sulfate, 30ml concentration are that 0.25M potassium peroxydisulfates and 10ml ammoniacal liquor are added sequentially to be used as deposition solution in 100ml beakers,
The aluminium doping zinc oxide nanometer rod array sample that will have been prepared, stand upright in above-mentioned deposition solution and carry out the deposition reaction of nickel source, 25
After being reacted 30 minutes under degree Celsius, sample is taken out, is annealed 1.5 hours in 350 degree of air.
A kind of 6. capacitor electrode material, based on the preparation method described in one of the claims 1-5, it is characterised in that institute
Electrode material is stated as aluminium-doped zinc oxide nano-array and the poorly conductive of the high conductivity prepared by continuous Flow Injection Analysis but
The high nickel oxide nano sheet material of capacitance combines gained.
7. electrode material according to claim 6, it is characterised in that the thickness of the nickel oxide nano sheet material is 100-
200nm。
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| CN107393654A (en) * | 2017-07-11 | 2017-11-24 | 扬州乾照光电有限公司 | A kind of method for the ZnO transparent conductive thin film that nanostructured is formed on substrate |
| CN107715890B (en) * | 2017-11-02 | 2019-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterogeneous ozone catalyst and products thereof and application |
| CN108597879B (en) * | 2018-03-19 | 2020-09-22 | 西北师范大学 | TiO 22Preparation method of nanowire/NiO nanosheet/porphyrin composite material |
Citations (2)
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| CN102368502A (en) * | 2011-10-13 | 2012-03-07 | 上海电力学院 | Zinc oxide film doped with Al and preparation method thereof |
| CN104020260A (en) * | 2014-06-18 | 2014-09-03 | 清华大学 | NiO and Al-doped ZnO heterogeneous nano structure as well as preparation method and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102368502A (en) * | 2011-10-13 | 2012-03-07 | 上海电力学院 | Zinc oxide film doped with Al and preparation method thereof |
| CN104020260A (en) * | 2014-06-18 | 2014-09-03 | 清华大学 | NiO and Al-doped ZnO heterogeneous nano structure as well as preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| "Au-Embedded ZnO/NiO Hybrid with Excellent Electrochemical Performance as Advanced Electrode Materials for Supercapacitor";Xin Zheng,et al.;《ACS Appl. Mater. Interfaces》;20150113;第7卷;第2480-2485页 * |
| "Electrical properties of rapid hydrothermal synthesised Al-doped zinc oxide nanowires in flexible electronics";Jang Bo Shim,et al.;《Micro & Nano Letters》;20110331;第6卷(第3期);第147-149页 * |
| "基于微通道内表面上垂直生长的ZnO纳米棒阵列的微反应器型光催化装置";何中媛等;《无机化学学报》;20091110;第25卷(第11期);第2021-2025页 * |
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