CN102942215A - Three-dimensional SnO2 nano flower-like material grown on titanium substrate and preparation method thereof - Google Patents
Three-dimensional SnO2 nano flower-like material grown on titanium substrate and preparation method thereof Download PDFInfo
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- CN102942215A CN102942215A CN2012103455033A CN201210345503A CN102942215A CN 102942215 A CN102942215 A CN 102942215A CN 2012103455033 A CN2012103455033 A CN 2012103455033A CN 201210345503 A CN201210345503 A CN 201210345503A CN 102942215 A CN102942215 A CN 102942215A
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- sodium hydroxide
- nano flower
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- titanium substrate
- stannic chloride
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Abstract
The invention discloses a three-dimensional SnO2 nano flower-like structural material grown on a titanium substrate and a preparation method thereof. Tetrachlorostannane pentahydrate and sodium hydroxide in a molar ratio of 1:3-16 are used as raw materials to grow the three-dimensional SnO2 nano flower-like structural material on the titanium substrate. The nano flower-like structural material has a simple preparation process and large specific surface area; and the preparation process can simplify preparation method of electrode, and is stable to acid and alkaline environment, and suitable for the fields of dye-sensitized solar cell, photocatalyst, gas sensor, capacitor and lithium ion battery.
Description
Technical field
The invention belongs to field of electrochemical energy storage materials, particularly a kind of D S nO that grows in the metal titanium substrate
2Nano flower-like material and preparation method thereof.
Background technology
SnO
2Be a kind of environmentally friendly N-shaped semi-conductor, energy gap is 3.6eV.Having very excellent chemistry, photoelectricity, gas sensing, optics and electrochemical properties, is the extraordinary multifunctional material of a kind of application prospect.SnO
2Has its huge using value and market potential at aspects such as photocatalyst, gas sensor, electrical condenser and lithium ion batteries, by countries in the world institute extensive concern.
In order to make material obtain more excellent performance, people are with SnO
2Be prepared into the nano material with various patterns, according to the literature SnO
2Successfully prepare nanometer sheet, nanotube, nanometer rod, nano wire and the nano belt of high-specific surface area.Yet these nano materials mostly prepare complexity (need additive or need template) and are powder body material, need to be compressed on equably on the collector the firm degree of using simultaneously some organic binder bonds to contact with collector to improve it, and SnO during application
2Relatively poor etc. electroconductibility, electric transmission speed is slower, also needs during compacting to mix with some conductive agents, and these means not only allow the part specific surface area of active material lose, and have reduced material property, also make electrode production process loaded down with trivial details.
And directly at the metal base SnO that grows
2Nano material then can be avoided the appeal problem, but at present to the SnO that grows in substrate
2The research of nano material is less, mainly contains following main representative: the people such as S.Ghosh (S.Ghosh, K.Das, K.Chakrabarti, et al, Template free synthesis of SnO
2Nanoflower arrays on Sn foil[J] .CrystEngComm, 2012,14:929-935) grow as the SnO of poppy flower at the tin metal sheet by solvent-thermal method
2Nano flower, but limit its practical application owing to metallic tin is unstable in soda acid; The people such as A.C.Chen (A.C.Chen, X.S.Peng, K.Koczkur, et al.Super-hydrophobic tin oxide nanoflowers[J] .Chem.Commun., 2004,1964-1965) by dibutyl tin dilaurate is sprayed on the titanium metal plate, prepare first the Sn nano flower by thermolysis process (350 ℃) pyrolysis dibutyl tin dilaurate on titanium metal plate again, then at high temperature (500 ℃) oxidation generates SnO
2Nano flower, this nano flower material skewness in the titanium substrate, its flower size is large, and diameter has about 100 microns, and the material specific surface area is just little comparatively speaking, therefore can reduce the contact area of material and reactive material, thereby affect material property, and the longer material of this method of spraying is combined shakiness with substrate, owing to whole preparation process need to be carried out under comparatively high temps, therefore the preparation method is complicated, and is also high to equipment requirements; The people such as T.Tsuchiya (T.Tsuchiya, K.Daoudi, I.Yamaguchi, et al.Preparation of tin oxide films on various substrates by excimer laser metal organic deposition[J] .Applied Surface Science, 2005,247:145-150) pass through excimer laser metal organogenous sediments with SnO
2Film preparation is (monocrystal silicon substrate, Sapphire Substrate, strontium titanate and TiO in various substrates
2Substrate), find in different substrates SnO
2The direction of growth of film is different, and the film of growth is not monocrystalline SnO simultaneously
2, but multicrystal, the whole lattice of monocrystalline is continuous, has important industrial application, as in lithium ion battery, the orderly crystal face of single crystal more helps the insertion of lithium ion and deviates from, thereby improves battery performance, so the SnO of this polycrystalline
2Film is difficult to apply.
Summary of the invention
Technical problem to be solved by this invention provides a kind of D S nO that grows in the metal titanium substrate
2Nano flower-like material and preparation method thereof, this D S nO
2The nano flower-like material is to be grown directly upon in the substrate of body titanium, and preparation technology is simple, has larger specific surface area, can simplify the preparation technology of electrode, and acid, alkaline environment are stablized.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
A kind of D S nO
2The nano flower-like structured material is raw material by stannic chloride pentahydrate and sodium hydroxide, the D S nO that generates in the metal titanium substrate
2The nano flower-like material, wherein the mol ratio of stannic chloride pentahydrate and sodium hydroxide is 1: 3～16.
The mol ratio of stannic chloride pentahydrate and sodium hydroxide optimization is 1: 15.
A kind of above-mentioned D S nO
2The preparation method of nano flower-like structured material comprises following step:
The processing of b, metal titanium substrate: the titanium sheet is cleaned 10min～20min in dilute hydrochloric acid, dehydrated alcohol and deionized water for ultrasonic respectively successively, and the titanium sheet after cleaning is dried is as substrate;
The configuration of b, precursor solution: a certain amount of sodium hydroxide is dissolved in the deionized water, after sodium hydroxide dissolves fully, stannic chloride pentahydrate is dissolved in the sodium hydroxide solution of preparation again, be mixed with the mixing solutions of stannic chloride pentahydrate and sodium hydroxide; Then magnetic agitation solution 20min, wherein the concentration range of stannic chloride pentahydrate is 0.1mol/L～0.4mol/L, the concentration range of sodium hydroxide is 1.2mol/L～1.6mol/L;
C, the titanium substrate that will soak through a step tilt place the polytetrafluoroethyllining lining of stainless steel cauldron, the mixing solutions of b step are transferred in this polytetrafluoroethyllining lining again;
D, stainless steel cauldron is placed baking oven, at 180～200 ℃ of lower reaction 8～24h;
The deionized water repetitive scrubbing is used in e, the reacted titanium substrate of taking-up, 60 ℃ of lower oven dry.
Compared with prior art, the technical program has following beneficial effect:
1. D S nO provided by the invention
2Nano flower-like structured material form is even, it is smooth to distribute, the nano flower diameter only has about 2 microns, the graceful approximate lotus of profile, distance is enough large between petal and petal, can well cushion the volumetric expansion in the lithium ion battery charge and discharge process, not only can improve the electronics transfer rate that participates in electrochemical reaction, high specific surface area also provides more effective active reaction site, has utilized to a greater degree SnO
2The nano flower-like structured material, the diffusion admittance of ion and electronics can improve electrode performance when three-dimensional nanostructure had shortened electrochemical reaction simultaneously, can be directly used in the energy storage material electrode, need not any conductive agent and tackiness agent, can greatly simplify technology for preparing electrode;
2. acid, alkaline environment are stablized; Can be applicable to various energy and materials, metal titanium and SnO
2With acid, alkaline medium H
2SO
4, chemical reaction all do not occur in HCl, NaOH, KOH, LiOH;
3. the present invention proposes first at the standby evenly SnO of titanium substrate previous step legal system
2The nano flower-like structured material is for the energy storage electrode material preparation provides Technical Reference;
4.SnO
2The nano flower-like material is firm in titanium substrate growth, and ultrasonic 30min still can not come off under high frequency, therefore can be applicable to the aspect higher to material requirements;
5. need not in the preparation process with an organic solvent and additive, technique is simple, and with low cost, is fit to batch production.
Description of drawings
Fig. 1 is the embodiment of the invention 5 gained SnO
2The field emission scanning electron microscope figure of nano flower-like structured material;
Fig. 2 is the embodiment of the invention 10 gained SnO
2The field emission scanning electron microscope figure of nano flower-like structured material;
Fig. 3 is the embodiment of the invention 11 gained SnO
2The field emission scanning electron microscope figure of nano flower-like structured material;
Fig. 4 is the embodiment of the invention 10 gained SnO
2The X-ray diffractogram of nano flower-like structured material;
Among Fig. 4:
(S:tin oxide): tindioxide;
(T:Ti substrate): titanium substrate;
(intensity/a.u.): intensity;
(2theta/degree): 2 θ/degree.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples do not consist of limitation of the invention
The below take the table in embodiment 10 as example, describe preparation method of the present invention in detail:
A. the processing of metal titanium substrate: with the titanium sheet of purity 99.6% after the oxide compound on surface is removed in the abrasive paper for metallograph polishing, ultrasonic cleaning 20min respectively in 8% hydrochloric acid, dehydrated alcohol, deionized water solution respectively is with further removal oxide on surface and corrosion substrate;
B. precursor solution preparation: 3.000gNaOH is dissolved in first the 50ml deionized water, again with the SnCl of 1.753g
45H
2O is dissolved in the just now NaOH solution of configuration, this solution is stirred 10min at 25 ℃ of condition lower magnetic forces form colourless transparent solution, the tin ion [Sn that obtains
4+] concentration is 0.1mol/L, hydroxide ion [OH
-] concentration is 1.5mol/L, the ratio [Sn of tin ion and hydroxide ion volumetric molar concentration
4+]/[OH
-The mixing solutions of]=1: 15;
C. the inclination of the titanium sheet among the step a (being 60 °, face down with inner liner of reaction kettle) is placed the polytetrafluoroethyllining lining of stainless steel cauldron, again the mixing solutions among the step b is transferred in this polytetrafluoroethyllining lining;
D. stainless steel cauldron is placed baking oven, at 200 ℃ of lower reaction 24h.
E. reaction is down to room temperature after finishing, with product deionized water repetitive scrubbing, 60 ℃ of lower oven dry.
The product of embodiment 5, embodiment 10 and embodiment 11 is carried out correlation detection
One, outward appearance
Can see that the titanium metal plate surface has formed one deck grey matter, is D S nO this moment
2The nano flower-like structured material.
Two, field emission scanning electron microscope analysis
As shown in Figure 1: embodiment 5 gained D S nO
2Nano flower-like structured material thickness is about 20～25nm, and its petal is about 0.8 μ m, wide about 400nm, and about 1 μ m is wide for whole flower;
As shown in Figure 2: embodiment 10 gained D S nO
2Nano flower-like structured material thickness is about 10～15nm, and its petal is about 1 μ m, wide about 300nm, and about 2 μ m are wide for whole flower, the graceful approximate lotus of profile, petal and petal spacing are larger, and are evenly distributed;
As shown in Figure 3: embodiment 11 gained D S nO
2Nano flower-like structured material thickness is about 15～20nm, and its petal is about 1.2 μ m, wide about 500nm, and about 1.5 μ m are wide for whole flower.
Three, X-ray diffraction scanning analysis
As shown in Figure 4: embodiment 10 gained D S nO
2Crystalline structure be the rutile-type crystalline structure.
Above-described only is preferred implementation of the present invention; should be understood that; for a person skilled in the art; under the prerequisite that does not break away from structure of the present invention; can also make some distortion and improvement; these also should be considered as protection scope of the present invention, and these can not affect effect of the invention process and practical applicability.
Claims (3)
1. D S nO
2The nano flower-like structured material is characterized in that, is raw material by stannic chloride pentahydrate and sodium hydroxide, the D S nO that generates in the metal titanium substrate
2The nano flower-like material, wherein the mol ratio of stannic chloride pentahydrate and sodium hydroxide is 1: 3～16.
2. D S nO as claimed in claim 1
2The nano flower-like structured material is characterized in that, the mol ratio of stannic chloride pentahydrate and sodium hydroxide is 1: 15.
3. above-mentioned D S nO
2The preparation method of nano flower-like structured material is characterized in that, comprises following step:
The processing of a, metal titanium substrate: the titanium sheet is cleaned 10min～20min in dilute hydrochloric acid, dehydrated alcohol and deionized water for ultrasonic respectively successively, and the titanium sheet after cleaning is dried is as substrate;
The configuration of b, precursor solution: a certain amount of sodium hydroxide is dissolved in the deionized water, after sodium hydroxide dissolves fully, stannic chloride pentahydrate is dissolved in the sodium hydroxide solution of preparation again, be mixed with the mixing solutions of stannic chloride pentahydrate and sodium hydroxide; Then magnetic agitation solution 20min, wherein the concentration range of stannic chloride pentahydrate is 0.1mol/L～0.4mol/L, the concentration range of sodium hydroxide is 1.2mol/L～1.6mol/L;
C, the titanium substrate that will soak through a step tilt place the polytetrafluoroethyllining lining of stainless steel cauldron, the mixing solutions of b step are transferred in this polytetrafluoroethyllining lining again;
D, stainless steel cauldron is placed baking oven, at 180～200 ℃ of lower reaction 8～24h;
The deionized water repetitive scrubbing is used in e, the reacted titanium substrate of taking-up, 60 ℃ of lower oven dry.
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Cited By (4)
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| CN105366714A (en) * | 2015-12-11 | 2016-03-02 | 暨南大学 | Synthetic method of stannic oxide nanoflower array |
| CN105967225A (en) * | 2016-05-13 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | {0><}0{>Tin dioxide nano flower and preparation method thereof |
| CN106757527A (en) * | 2017-02-16 | 2017-05-31 | 济南大学 | The preparation method and products obtained therefrom of a kind of compound micro-flowers of SnO2/C |
| CN106848278A (en) * | 2017-01-10 | 2017-06-13 | 广西大学 | The preparation method of metallic compound nano structural membrane material |
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| CN101613080A (en) * | 2009-07-23 | 2009-12-30 | 重庆大学 | A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366714A (en) * | 2015-12-11 | 2016-03-02 | 暨南大学 | Synthetic method of stannic oxide nanoflower array |
| CN105967225A (en) * | 2016-05-13 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | {0><}0{>Tin dioxide nano flower and preparation method thereof |
| CN105967225B (en) * | 2016-05-13 | 2018-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of stannic oxide nanometer flower and preparation method thereof |
| CN106848278A (en) * | 2017-01-10 | 2017-06-13 | 广西大学 | The preparation method of metallic compound nano structural membrane material |
| CN106757527A (en) * | 2017-02-16 | 2017-05-31 | 济南大学 | The preparation method and products obtained therefrom of a kind of compound micro-flowers of SnO2/C |
| CN106757527B (en) * | 2017-02-16 | 2018-11-23 | 济南大学 | A kind of preparation method and products obtained therefrom of the compound micro-flowers of SnO2/C |
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Application publication date: 20130227 |