CN102534781A

CN102534781A - Ti-doped titanium dioxide nanowire array, as well as preparing method and application of Ti-doped titanium dioxide nanowire array

Info

Publication number: CN102534781A
Application number: CN2012100437616A
Authority: CN
Inventors: 郑耿锋; 胥明; 吴昊宇
Original assignee: Fudan University
Current assignee: Fudan University
Priority date: 2012-02-25
Filing date: 2012-02-25
Publication date: 2012-07-04

Abstract

The invention belongs to the technical field of solar cells, in particular to a Ti-doped titanium dioxide nanowire array capable of photolyzing water efficiently, as well as a preparing method and the application of the Ti-doped titanium dioxide nanowire array. The preparing method comprises the following steps: taking tetrabutyl titanate as a Ti source, water as a solvent, and stannic chloride as an Sn source under a hydrothermal system; adding concentrated hydrochloric acid to regulate and control the hydration reaction speed; growing a Ti-doped titanium dioxide nano-wire array on an electro-conductive glass substrate made of FTO (fluorine-doped tin oxide); and carrying out heat treatment in an argon-hydrogen mixture gas or a nitrogen-hydrogen mixture gas. The technology has the advantage that the conventional water photolyzing technology and the conventional photoelectric conversion technology are coupled, so as to improve the light absorption efficiency of a solar cell, and realize the one-step process of efficient water photolyzing and photoelectric photocurrent conversion. The invention further has the advantages that the raw material sources are wide; the preparing method is simple and environment-friendly; the cost is low; and the popularization and the application are more convenient.

Description

Mix the tin titanium dioxide nanowire array

Technical field

The invention belongs to technical field of solar batteries, what be specifically related to a kind of efficient photodissociation water mixes tin titanium dioxide nanowire array and preparation method thereof and the application in solar cell.

Background technology

The energy has received each national great attention as lifeblood and the power of social development of world economy in this century.China's energy demand total amount is big and rate of growth is fast, has become second largest Energy production state and the country of consumption that is only second to the U.S. in the world at present.Yet its reserves of fossil oil that account for world energy sources supply 90% are exhausted day by day, and the use of fossil oil has also caused problems such as serious environmental pollution and Greenhouse effect.So the many ground of People more and more have turned to cleaning, reproducible new forms of energy with sight.Sun power is primary energy source as the source of energy on the earth, is again renewable energy source.Its aboundresources both can freely use, and need not transportation again, and environment is not had any pollution, therefore received increasing people's concern, had also promoted developing rapidly of solar battery technology.

It mainly is two general orientation that people utilize the approach of sun power, and one is photolysis water hydrogen, and another is that photoelectricity transforms the generation photoelectric current.Photoelectricity transforms the generation photoelectric current can directly be used for power supply, and the hydrogen that photolysis water hydrogen produces can be used as new forms of energy again and realizes staggering the time power supply.Therefore, seek the important front edge direction that efficient stable, environmental friendliness, the material that can be applicable to solar cell that efficient is high become current research.At present the broad research material mainly contain transition metal oxide and sulfide, the poor stability of sulfide comparatively speaking, oxide compound efficient is on the low side.Common oxide compound comprises zinc oxide, Tungsten oxide 99.999, red stone, titanium oxide etc., and is wherein maximum to the research of titanium oxide.Shortcomings such as but titanium oxide is wide band gap semiconducter (energy gap is 3.2 eV), and main absorbing ultraviolet light exists light induced electron-hole short to the life-span in addition, and the photocatalytic process quantum yield is low.In order to improve the efficient of titanium dioxide optical catalyst, can improve the responsiveness of titanium oxide through methods such as doping or finishinges, thereby improve the photochemical catalysis quantum yield light.

Summary of the invention

The purpose of this invention is to provide a kind of efficient photolysis water hydrogen that has, what produce photoelectric current simultaneously mixes the tin titanium dioxide nanowire array.

The preparation method who mixes the tin titanium dioxide nanowire array provided by the invention, concrete steps are:

(1) water was mixed 0.1 – after 0.5 hour with concentrated acid, to wherein adding titanium source, Xi Yuan; After whipped state reacts 5 –, 10 min down; Transfer in the reaction kettle, substrate (like the FTO conductive glass) face down of suitable size is put into still, reaction 4 – 20 hours under 180 ℃ of conditions of 140 –;

(2) product that above-mentioned steps is made is rinsed well, is dried; Roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere; Then roasting 0.5 – 2 hours under 550 ℃ of temperature parts of 350 – in rare gas element and reducing gas mixed atmosphere can obtain to mix the tin titanium dioxide nanowire array.

Described titanium source can be one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, propyl carbinol titanium, tetrem amido titanium, four Propylamino titaniums or the four butylamine base titaniums.

Described tin source can be a kind of of tin tetrachloride, tin acetate.

Described concentrated acid can be concentrated hydrochloric acid or nitric acid.

Described rare gas element can be nitrogen, argon gas or helium.

Described reducing gas can be reducing gas such as hydrogen or methane.

Described substrate can be silicon chip or the slide that FTO glass or spin coating have the titanium oxide crystal seed.

Among the present invention, mix in the tin titanium dioxide nanowire array, mixing the tin amount is total mass 0.5 – 2%.Mix the tin titanium dioxide nanowire array and can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current.

Nano-wire array of the present invention can be applicable to solar cell: to mix the tin titanium dioxide nanowire array is working electrode; The Ag/AgCl electrode is a reference electrode; Platinum filament is a counter electrode; 0.1 the sodium hydroxide of – 1 M or potassium hydroxide solution are reaction soln, irradiates light intensity is a sunshine, and the irradiation sectional area is can be according to the area size adjustment of working electrode.

The tin titanium dioxide array of mixing of the present invention is to adopt Hydrothermal Preparation, prepares titanium dioxide nanowire array through the doping of an amount of tin, realizes that efficient photolysis water hydrogen produces the performance of photoelectric current simultaneously.Mixing the tin titanium dioxide nanowire array, to have manufacture craft simple, and cost is low, good stability; High and the environment amenable characteristics of electricity conversion; Be fit to big area production, upward significant for solar cell research, also have good application prospects at new energy field.

Description of drawings

Fig. 1: A – C is the SEM photo of the different tin dope titanium dioxide nano thread of density; D is the side SEM photo of B figure; E is the TEM photo of single nano-wire.

Fig. 2: A is photoelectric current curve (solid line) and a dark current curve (dotted line) of mixing tin titanium oxide; B be under 0V vs Ag/AgCl condition time-the photoelectric current curve.

Fig. 3 is applied to the solar cell diagram for the tin dope titanium dioxide nanowire array.

Embodiment

Below, through following examples the present invention being described further, it will help to understand the present invention, but not limit content of the present invention.

At first FTO glass is placed the reaction kettle of 50 ml, face down is got 15 ml water and is mixed with 13 ml concentrated hydrochloric acids, then in it, adds the SnCl of 0.25 ml tetra-n-butyl titanate and 0.2 ml, 0.1 M ₄Solution.The change of wherein acid amount can influence the density (like Fig. 1) of preparation nano wire.Treated solution stirring 5 – 10 minutes, and after mixing, poured in the reaction kettle that reaction is 12 hours under 150 ℃ of conditions.After reaction finishes, the substrate taking-up is cleaned and dried up.Then, substrate was placed in the tube furnace under 450 ℃ of conditions roasting 2 hours, further, the continuation roasting is 0.5 hour under the hydrogen of 150 sccm and argon gas mixed atmosphere.At last, under argon shield, reduce to room temperature.

As shown in Figure 3, be working electrode to mix the tin titanium dioxide nanowire array, the Ag/AgCl electrode is a reference electrode, and platinum filament is a counter electrode, and the sodium hydroxide solution of 0.1 –, 1 M is a reaction soln, and irradiates light intensity is a sunshine, irradiated area is 1 cm ²Under the 0V condition, survey its photoelectricity flow valuve, can find that photoelectric current is about 1.8 mA (like Fig. 2 A).Surpass 10 hours when sweep time, the photoelectricity flow valuve still keeps stable (like Fig. 2 B).

Claims

One kind can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current mix the tin titanium dioxide nanowire array, wherein mixing the tin amount is 0.5 – 2% of total mass.
2. the preparation method who mixes the tin titanium dioxide nanowire array that can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current as claimed in claim 1 is characterized in that concrete steps are:

(1) water was mixed 0.1 – after 0.5 hour with concentrated acid, to wherein adding titanium source, Xi Yuan; After whipped state reacts 5 –, 10 min down; Transfer in the reaction kettle, the substrate front surface of suitable size is put into still down, reaction 4 – 20 hours under 180 ℃ of conditions of 140 –;

(2) product that above-mentioned steps is made is rinsed well, is dried; Roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere; Then roasting 0.5 – 2 hours under 550 ℃ of temperature condition of 350 – in rare gas element and reducing gas mixed atmosphere can obtain to mix the tin titanium dioxide nanowire array.
3. preparation method as claimed in claim 2 is characterized in that described concentrated acid is concentrated hydrochloric acid or nitric acid.
4. preparation method as claimed in claim 2 is characterized in that described titanium source is one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, tetra-n-butyl titanate, tetrem amido titanium, four Propylamino titaniums or the four butylamine base titaniums.
5. preparation method as claimed in claim 2 is characterized in that described Xi Yuan is tin tetrachloride or tin acetate.
6. preparation method as claimed in claim 2 is characterized in that described rare gas element is nitrogen, argon gas or helium.
7. preparation method as claimed in claim 2 is characterized in that described reducing gas is hydrogen or methane.
8. preparation method as claimed in claim 2 is characterized in that described substrate is silicon chip or the slide that FTO glass or spin coating have the titanium oxide crystal seed.
9. as claimed in claim 1 can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current mix the application of tin titanium dioxide nanowire array in the preparation solar cell.