CN103208371B - A kind of material for solar cell - Google Patents
A kind of material for solar cell Download PDFInfo
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- CN103208371B CN103208371B CN201310079027.XA CN201310079027A CN103208371B CN 103208371 B CN103208371 B CN 103208371B CN 201310079027 A CN201310079027 A CN 201310079027A CN 103208371 B CN103208371 B CN 103208371B
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Abstract
The invention discloses a kind of material for solar cell, the technical scheme of employing is as follows: by upper conversion ultra-violet light-emitting material Er
3+: YAlO
3/ TiO
2or Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2composite membrane be used for the electrode material of solar cell, Er in composite membrane
3+: YAlO
3or Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2mass ratio is 1:9 ~ 3:7; Lift infusion process is adopted to prepare Er
3+: YAlO
3/ TiO
2composite membrane and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane.Er prepared by the present invention
3+: YAlO
3/ TiO
2composite membrane and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane stable in properties, makes simple, with simple TiO
2film is compared, and significantly can promote the utilance of solar energy, the photoelectric conversion efficiency of solar cell is significantly improved, also can be used for environmental protection and the energy fields such as air cleaning, waste water treatment and photolysis water hydrogen, have a extensive future.
Description
Technical field
The invention belongs to solar cell material field, relate to a kind of Er of high visible-light activity particularly
3+: YAlO
3/ TiO
2composite membrane and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of composite membrane is also applied in the electrode material of solar cell.
Background technology
Along with the development of global economy and the sharply increase of population, the demand of the mankind to the energy rapidly increases, and the energy crisis caused thus and environmental pollution become serious problems urgently to be resolved hurrily.On the one hand, current world energy supplies mainly relies on coal, oil, the fossil energies such as natural gas, these fossil energy essence are that before tens thousand of year, even the longer time is evolved into tellurian energy mineral reserve today through the change that time brings great changes to the world, and the consumption of experience mankind last 100 years has irreversibly moved towards exhausted.According to the prediction of the world energy sources committee, oil will be exhausted after 43 years, and natural gas will be used up after 66 years, and the maximum coal of stock number also only enough uses 169 years.On the other hand, the development and utilization of fossil energy can cause serious environmental pollution and ecological disruption, produces serious harm to the living environment of the mankind and other biology.And the greenhouse effect that the carbon dioxide that produces of the environmental pollution that causes of the exploitation of fossil fuel and burning causes, change the living environment of the mankind and other biology greatly, make us face unprecedented challenge.Therefore, a kind of new energy is found just to seem particularly important.Seek environmental friendliness, clean and reproducible green energy resource, such as: solar energy, wind energy, biological energy source, water energy, Hydrogen Energy and geothermal energy etc., become the focus of people's extensive concern.In all fungible energy source, solar energy is abundant, safety, acquisition are convenient, and the research being therefore particularly converted into electric energy to solar energy to the exploitation of solar energy causes the extensive concern of people.
Solar energy is the regenerative resource the most widely that distributes, and solar energy takes up an area ball gross energy more than 99%.According to measuring and calculating, the energy equivalence that the sun discharges each second is in burning 1.28 hundred million tons of energy that standard coal is released, and the energy being radiated earth surface is every year about 17,000,000,000,000 kilowatt hours, is equivalent to 3.5 ten thousand times of the 1 year energy total flow in the current whole world; In addition, compared with other energy, solar energy has by advantages such as geographical conditions restriction, safety, efficient, clean, low costs.Therefore, no matter be from current demand, or from the development potentiality in future, in all kinds of regenerative resource, solar energy is all the first-selection that countries in the world are developed.The countries such as the U.S., Japan, Germany have all promulgated corresponding laws and regulations, encourage to use the regenerative resources such as solar energy.China is the fastest-rising country of energy-consuming in the world, is also SO
2, NO, CO
2discharge big country, the pressure of environmental pollution is more and more large.
Be that the Solar use supported brings revolutionary change to the energy consumption structure of the mankind with solar-photovoltaic technology.The Olympic Games of 2008, Beijing becomes the maximum impression window of China in Application of Solar Energy, and the new ideas that " new olympic " fully demonstrates " the environmental protection Olympic Games, the energy-conservation Olympic Games ", around the Olympic stadiums, the street lamp of 80% ~ 90% utilizes solar photovoltaic technology.Solar cell is a kind of common form of our times development and utilization solar energy, there is not consume fuel, do not limit by region, scale can flexible combination, pollution-free, noiselessness, safe and reliable, safeguard simple, the advantages such as the construction period is short, have most the possibility of large-scale application, it utilizes photovoltaic effect solar energy to be converted to electric energy to use to supply user.Solar cell is one of global fastest-rising high-tech industry, the 100KW that its output has begun by 1971, and the speed increase by annual 10% so far.Widely, application comprises the electrification of the countryside, traffic, communication, oil, meteorology, national defence etc. to the range of application of solar cell.Photovoltaic power supply system solves the electricity consumptions such as many rural schools, infirmary, domestic lighting, TV, has played very important effect to the social economy of development outlying poverty-stricken area with culture.China Tibet has 7 to adopt photovoltaic plant to power without electric county town, economic results in society highly significant.
At present, more commonly silicon solar cell on market, its highest transformation efficiency can reach about 25%.But complex manufacturing technology, the shortcomings such as cost intensive limit its further commercialization and widely use.Through exploring for a long time, nano-TiO
2semiconductor is because having larger energy gap and stable fast light corrosivity and being considered to the optoelectronic pole material of the solar cell of great potential.Therefore, since entering 21st century, nano-TiO
2the research of solar cell becomes focus.But, nano-TiO
2the electrode of assembling is due to comparatively large (the anatase type nano TiO of energy gap
2energy gap be 3.12eV), can only ultraviolet light be absorbed, to only containing lower less than the utilance of the solar energy of 5% ultraviolet light, cause its photoelectric conversion efficiency lower, so be used alone nano-TiO
2there is serious shortcomings in assembling electrode.
Summary of the invention
In order to solve nano-TiO
2first-selected catalyst photocatalysis efficiency as solar battery group loading electrode is not high, and wavelength must be adopted to be less than the problem of the UV-irradiation of 387nm, an object of the present invention be to provide a kind of can by the upper conversion ultra-violet light-emitting material Er of visible ray and infrared light
3+: YAlO
3with TiO
2compound, preparation Er
3+: YAlO
3/ TiO
2composite membrane is for making the electrode material of solar cell.
Another object of the present invention adopts the method for doping to upper conversion ultra-violet light-emitting material Er
3+: YAlO
3improve, preparation Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane is for making the electrode material of solar cell.
The technical solution used in the present invention is: a kind of material for solar cell, by upper conversion ultra-violet light-emitting material and TiO
2composite membrane for making the electrode material of solar cell.
Above-mentioned a kind of material for solar cell, described upper ultra-violet light-emitting material of changing is into Er
3+: YAlO
3or Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8, Er in described composite membrane
3+: YAlO
3or Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2mass ratio is 1:9 ~ 3:7.
Er
3+: YAlO
3/ TiO
2the preparation method of composite membrane is as follows:
1) Er is prepared
3+: YAlO
3/ TiO
2complex sol: get the Er that mass ratio is 1:9 ~ 3:7
3+: YAlO
3nanometer powder and TiO
2colloidal sol, stirs, and leaves standstill, obtains target product Er
3+: YAlO
3/ TiO
2complex sol;
2) Er is prepared
3+: YAlO
3/ TiO
2composite membrane: electro-conductive glass sheet is dipped vertically into above-mentioned Er
3+: YAlO
3/ TiO
2in complex sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet at the uniform velocity reposefully from Er
3+: YAlO
3/ TiO
2take out dry in complex sol, obtain one deck composite membrane, repeated impregnations, lift, dry, obtain multilayer complex films, heated 30 ~ 60 minutes by composite membrane under 300 ~ 600 ° of C, cooling, obtains Er
3+: YAlO
3/ TiO
2composite membrane.
Above-mentioned Er
3+: YAlO
3/ TiO
2the preparation method of composite membrane, described Er
3+: YAlO
3the preparation method of nanometer powder is as follows: by chemical molecular formula Er
3+: YAlO
3in each element proportioning be converted into Er
2o
3, Y
2o
3with Al (NO
3)
39H
2o feeding, by Er
2o
3and Y
2o
3be dissolved in red fuming nitric acid (RFNA), magnetic agitation also heats until water white transparency, obtains A liquid; Then Al (NO is taken in proportion
3)
39H
2o and citric acid, dissolve with distilled water, the mol ratio of citric acid and rare earth ion is 3:1, obtains B liquid; Room temperature, slowly joins in A liquid by B liquid under stirring, then stirs under 50 ~ 60 ° of C and obtains colloidal sol in 1 ~ 2 hour, heat 32 ~ 38 hours under 80 ° of C, obtain gel, after the gel obtained is heated 50 minutes under 500 ° of C, be warming up to 1100 ° of C and calcine 120 minutes, obtain Er
3+: YAlO
3nanometer powder.
Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation method of composite membrane is as follows:
1) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of complex sol: get the Er that mass ratio is 1:9 ~ 3:7
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder and TiO
2colloidal sol, stirs, and leaves standstill, obtains target product Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2complex sol;
2) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of composite membrane: electro-conductive glass sheet is dipped vertically into above-mentioned Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2in complex sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet at the uniform velocity reposefully from Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2take out dry in complex sol, obtain one deck composite membrane, repeated impregnations, lift, dry, obtain multilayer complex films, heated 30 ~ 60 minutes by composite membrane under 300 ~ 600 ° of C, cooling, obtains Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane.
Above-mentioned Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation method of composite membrane, described Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8the preparation method of nanometer powder is: by chemical molecular formula Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2in each element proportioning be converted into Er
2o
3, Yb
2o
3, Y
2o
3, Al (NO
3)
39H
2o, urea and hydrofluoric acid quality than feeding, by Er
2o
3, Yb
2o
3and Y
2o
3be dissolved in red fuming nitric acid (RFNA), then add urea and hydrofluoric acid solution in solution, magnetic agitation also heats until water white transparency, obtains A liquid; Then Al (NO is taken in proportion
3)
39H
2o and citric acid, dissolve with distilled water, the mol ratio of citric acid and rare earth ion is 3:1, obtains B liquid; Room temperature, slowly joins in A liquid by B liquid under stirring, then stirs under 50 ~ 60 ° of C and obtains colloidal sol in 1 ~ 2 hour, heat 32 ~ 38 hours under 80 ° of C, obtain gel, after the gel obtained is heated 50 minutes under 500 ° of C, be warming up to 1100 ° of C and calcine 120 minutes, obtain Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder.
Er
3+: YAlO
3/ TiO
2composite membrane is as follows as the principle of solar cell efficiency utilization solar energy: well-known, containing the visible ray of 45% and the infrared light of 50% in sunlight, but only contains the ultraviolet light less than 5%.As visible ray direct irradiation TiO
2time, due to broader bandwidth (Eg=3.20eV), the visible ray in sunlight effectively can not excite TiO
2particle produces electron-hole pair.But, when radiation of visible light is to upper conversion ultra-violet light-emitting material Er
3+: YAlO
3after, due to Er
3+: YAlO
3under visible light illumination, ground state photon can be energized into higher energy level step by step electronics, and then these photons are after ground state is returned in transition again, and launch high-octane ultraviolet light, these ultraviolet luminous energy excite Er effectively
3+: YAlO
3tiO around nano particle
2particle, through the TiO excited
2electronics in valence band (VB) can be delivered on conduction band (CB), thus formation has high-octane electron-hole pair.The present invention also utilizes upconversion UV luminescent material of broadband spectral adsorption Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8, to greatest extent the infrared light in sunlight and visible ray can be transformed into TiO
2utilizable ultraviolet light.The Er of high performance solar batteries is prepared based on this principle
3+: YAlO
3/ TiO
2and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite film material.
beneficial effect of the present invention:
Er prepared by the present invention
3+: YAlO
3/ TiO
2composite membrane, stable in properties, makes simple, with simple TiO
2thin-film solar cells is compared, and significantly improves the photo-quantum efficiency that visible ray utilizes.Compared to traditional TiO
2thin-film solar cells, Er in the present invention
3+: YAlO
3/ TiO
2the solar cell that composite membrane makes it is worth noting owing to there being upper conversion ultra-violet light-emitting material Er most
3+: YAlO
3add, make TiO
2the Solar use efficiency of composite membrane increases substantially.The particularly upper conversion ultra-violet light-emitting material Er of different element doping
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2the composite membrane formed has higher Solar use efficiency, as a kind of solar cell material of efficiency utilization solar energy, and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane will be with a wide range of applications.
Accompanying drawing illustrates:
Fig. 1 .Er
3+: YAlO
3(Er:YAP) nanometer powder and Er
3+: YAlO
3/ TiO
2(Er:YAP/TiO
2) XRD of composite membrane.
Fig. 2 .Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8(Er:Yb, N, F-doped-YAP) nanometer powder and Er
3+: Yb
0.2y
0.79alN
0.1f
0.1o
2.8/ TiO
2(Er:Yb, N, F-doped-YAP/TiO
2) XRD of composite membrane.
Fig. 3. adopt different Er
3+: YAlO
3and TiO
2the Er that quality obtains
3+: YAlO
3/ TiO
2the electric current that composite membrane produces under visible light illumination and voltage (a:TiO
2; B:(1:9) Er
3+: YAlO
3/ TiO
2; C:(3:7) Er
3+: YAlO
3/ TiO
2.).
The electric current that the Er3+:YAlO3/TiO2 composite membrane that Fig. 4-1.300 ° of C calcination temperatures obtain produces under visible light illumination and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.); The electric current that the Er3+:YAlO3/TiO2 composite membrane that Fig. 4-2.500 ° of C calcination temperatures obtain produces under visible light illumination and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.).
Fig. 5-1. calcination time is the electric current that produces under visible light illumination of Er3+:YAlO3/TiO2 composite membrane that obtains of 30min and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.); Fig. 5-2. calcination time is the electric current that produces under visible light illumination of Er3+:YAlO3/TiO2 composite membrane that obtains of 60min and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.).
The electric current that Fig. 6-1.Er3+:YAlO3/TiO2 composite membrane produces under the radiation of visible light of 30W and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.); The electric current that Fig. 6-2.Er3+:YAlO3/TiO2 composite membrane produces under 90W radiation of visible light and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.).
The electric current that the Er3+:YAlO3/TiO2 composite membrane of Fig. 7-1. one deck produces under visible light illumination and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.); The electric current that the Er3+:YAlO3/TiO2 composite membrane that Fig. 7 is-2. two layers produces under visible light illumination and voltage (a:TiO2; B:(3:7) Er3+:YAlO3/TiO2.).
Fig. 8. the Er of different sequence
3+: YAlO
3/ TiO
2the electric current that composite membrane produces under visible light illumination and voltage (a: two-layer TiO
2; B: ground floor Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2, second layer TiO
2; C: ground floor TiO
2, second layer Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2.
Fig. 9. adopt the Er that different doped chemical obtains
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electric current that composite membrane produces under visible light illumination and voltage (a:TiO
2; B:(3:7) Er
3+: YAlO
3/ TiO
2; C:(3:7) Er
3+: Yb
0.2yAlN
0.1f
0.1n
2.8/ TiO
2.).
Embodiment
embodiment 1Er
3+
: YAlO
3
/ TiO
2
composite membrane and Er
3+
: Yb
0.2
y
0.79
n
0.1
f
0.1
alO
2.8
/ TiO
2
the preparation of composite membrane
1, TiO
2film and Er
3+: YAlO
3/ TiO
2the preparation of composite membrane
(1) upper conversion ultra-violet light-emitting material Er
3+: YAlO
3the preparation of nanometer powder
0.0012g erbium oxide (Er is taken with electronic balance
2o
3) powder and 0.6820g yttria (Y
2o
3) powder joins in 25mL red fuming nitric acid (RFNA), magnetic force adds thermal agitation until water white transparency, obtains A liquid; Take 2.2658g aluminum nitrate (Al (NO
3)
39H
2and 7.6162g citric acid (C O)
6h
8o
7h
2o), dissolve with 100mL distilled water, obtain B liquid.Under stirring at room temperature, B liquid is slowly joined in A liquid; Then be warming up to 50 ° of C, magnetic agitation reacts 2 hours, stops when solution is thick, finally obtain the glutinous colloidal solution that foams, solution after reaction is put into baking oven, and constant temperature 80 ° of C heat and obtain gel in 36 hours, fully after grinding, the gel dry powder obtained 500 ° of C in Muffle furnace are heated 50 minutes, then 1100 ° of C are warming up to, calcine 120 minutes, finally, from Muffle furnace, take out the material of sintering, be cooled to room temperature in atmosphere, grinding obtains Er
3+: YAlO
3nanometer powder.
(2) TiO
2colloidal sol and Er
3+: YAlO
3/ TiO
2the preparation of complex sol
After 10mL butyl titanate is dissolved in 30mL ethanol, dropwise add the mixed solution of 10mL ethanol, 0.9mL distilled water and 1.4mL glacial acetic acid, stir 2.0 hours, obtain TiO
2colloidal sol.
By Er
3+: YAlO
3and TiO
2mass ratio is 3:7, by Er
3+: YAlO
3nanometer powder joins TiO
2in colloidal sol, stir 1.0 hours, leave standstill 1.0 hours, obtain the Er that mass ratio is 3:7
3+: YAlO
3/ TiO
2complex sol.
By Er
3+: YAlO
3and TiO
2mass ratio is 1:9, by Er
3+: YAlO
3nanometer powder joins TiO
2in colloidal sol, stir 1.0 hours, leave standstill 1.0 hours, obtain the Er that mass ratio is 1:9
3+: YAlO
3/ TiO
2complex sol.
(3) TiO
2film and Er
3+: YAlO
3/ TiO
2the preparation of composite membrane
Electro-conductive glass sheet first with water cleaning, is then used Ultrasonic Cleaning process in ethanol, electro-conductive glass sheet is dipped vertically into TiO respectively
2in colloidal sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet take out, after drying, obtain being coated with 1 layer of TiO
2film, repeated impregnations, lift, dry, what obtain is coated with 2 layers of TiO
2film, 1 layer of TiO will be coated with
2the electro-conductive glass sheet of film and be coated with 2 layers of TiO
2the electro-conductive glass sheet of film puts into Muffle furnace respectively, heat treated 60 minutes under 500 ° of C, naturally cools, obtains 1 layer of TiO
2film and 2 layers of TiO
2film.
Electro-conductive glass sheet first with water cleaning, is then used Ultrasonic Cleaning process in ethanol, electro-conductive glass sheet is dipped vertically into respectively the Er of above-mentioned different quality ratio
3+: YAlO
3/ TiO
2in complex sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet take out, after drying, obtain being coated with 1 layer of Er
3+: YAlO
3/ TiO
2composite membrane, repeated impregnations, lift, dry, what obtain is coated with 2 layers of Er
3+: YAlO
3/ TiO
2composite membrane, by 1 layer of Er
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of composite membrane and 2 layers of Er
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of composite membrane puts into Muffle furnace respectively, heat treated 60 minutes under 500 ° of C, naturally cools, finally obtains 1 layer of Er
3+: YAlO
3/ TiO
2composite membrane and 2 layers of Er
3+: YAlO
3/ TiO
2composite membrane.
Electro-conductive glass sheet first with water cleaning, is then used Ultrasonic Cleaning process in ethanol, electro-conductive glass sheet is dipped vertically into TiO respectively
2in colloidal sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet take out, after drying, obtain being coated with the pure TiO of one deck
2the sheet glass of gel mould, then will be coated with the pure TiO of one deck
2the electro-conductive glass sheet of gel mould is immersed in Er again
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2in complex sol, obtaining ground floor is pure TiO
2, the second layer is Er
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of plural gel film, the electro-conductive glass sheet being coated with plural gel film is put into Muffle furnace, heat treated 60 minutes under 500 ° of C, naturally cool, finally obtaining ground floor is pure TiO
2, the second layer is Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2composite membrane.
(4) Er
3+: YAlO
3nanometer powder and Er
3+: YAlO
3/ TiO
2the XRD analysis of composite membrane
With the Er that X-ray powder diffractometer measures
3+: YAlO
3nanometer powder and 1 layer of Er
3+: YAlO
3/ TiO
2the XRD of composite membrane as shown in Figure 1.Er
3+: YAlO
3/ TiO
2er has been there is in the XRD of composite membrane
3+: YAlO
3nanometer powder X-ray powder diffraction peak, Er
3+: YAlO
3/ TiO
2the characteristic peak of composite membrane and Er
3+: YAlO
3xRD standard peak position compare and have small change.In addition, at Er
3+: YAlO
3/ TiO
2have a new peak to appear at 2 θ=25.5 ° in the XRD of composite membrane, this is anatase titanium dioxide TiO
2characteristic peak, and Er
3+: YAlO
3peak all die down, this shows Er
3+: YAlO
3/ TiO
2containing Er in composite membrane
3+: YAlO
3and TiO
2and compound is better.
2, Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of composite membrane
(1) upper conversion ultra-violet light-emitting material Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8the preparation of nanometer powder
0.0105g erbium oxide (Er is taken with electronic balance
2o
3) powder, 0.2170g yttria (Yb
2o
3) and 0.4912g yttria (Y
2o
3) powder joins in 25mL red fuming nitric acid (RFNA), then in solution, add 0.0165g urea (CO (NH
2)
2) and 0.016mlHF(40%) solution, magnetic force adds thermal agitation until water white transparency, obtains A liquid; Take 2.066g aluminum nitrate (Al (NO
3)
39H
2and 6.9441g citric acid (C O)
6h
8o
7h
2o), dissolve with 100mL distilled water, obtain B liquid; Room temperature, slowly joins in A liquid by B liquid under stirring; Then be warming up to 50 ° of C, magnetic agitation reacts 2 hours, stops when solution is thick, finally obtain the glutinous colloidal solution that foams, solution after reaction is put into baking oven, and constant temperature 80 ° of C heat 36 hours, obtain gel, after abundant grinding, the gel dry powder obtained 500 ° of C in Muffle furnace are heated 50 minutes, be then warming up to 1100 ° of C, calcine 120 minutes, finally, from Muffle furnace, take out the material of sintering, be cooled to room temperature in atmosphere, grinding obtains Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder.
(2) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of compound colloidal sol
After 10mL butyl titanate is dissolved in 30mL ethanol, dropwise add the mixed solution of 10mL ethanol, 0.9mL distilled water and 1.4mL glacial acetic acid, stir 2.0 hours, obtain TiO
2colloidal sol.
By Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8and TiO
2mass ratio is 3:7, by Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder joins TiO
2in colloidal sol, stir 1.0 hours, leave standstill 1.0 hours, obtain the Er that mass ratio is 3:7
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2compound colloidal sol.
By Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8and TiO
2mass ratio is 1:9, by Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder joins TiO
2in colloidal sol, stir 1.0 hours, leave standstill 1.0 hours, obtain the Er that mass ratio is 1:9
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2compound colloidal sol.
(3) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of composite membrane
Electro-conductive glass sheet first with water cleaning, is then used Ultrasonic Cleaning process in ethanol, electro-conductive glass sheet is dipped vertically into above-mentioned Er respectively
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2in complex sol, leave standstill after 1.0 minutes, with 0.6cms
1pull rate by electro-conductive glass sheet take out, after drying, what obtain is coated with one deck Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electro-conductive glass sheet of plural gel film, repeated impregnations, lift, dry, what obtain is coated with two layers of Er
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of plural gel film, will be coated with one deck Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electro-conductive glass sheet of plural gel film and be coated with two layers of Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electro-conductive glass sheet of plural gel film puts into Muffle furnace respectively, heat treated 60 minutes under 500 ° of C, naturally cools, obtains one deck Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane and two layers of Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electro-conductive glass sheet of composite membrane.
(4) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the XRD analysis of composite membrane
With the Er that X-ray powder diffractometer measures
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder and 1 layer of Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the XRD of composite membrane as shown in Figure 2.Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2er has been there is in the XRD of composite membrane
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder X-ray powder diffraction peak.Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the characteristic peak of composite membrane and Er
3+: YAlO
3xRD standard peak position compare and have small change.In addition, at Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2have a new peak to appear at 2 θ=25.5 ° in the XRD of composite membrane, this is anatase titanium dioxide TiO
2characteristic peak, and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8peak all die down, this shows Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2containing Er in composite membrane
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8and TiO
2and compound is better.
er prepared by embodiment 2 different condition
3+
: YAlO
3
/ TiO
2
composite membrane is used for TiO
2
the Performance comparision of solar cell
1, the Er of different quality ratio
3+: YAlO
3/ TiO
2composite membrane is used for TiO
2the performance comparison of solar cell
Experiment condition: get one deck Er that mass ratio is 1:9 and 3:7 respectively
3+: YAlO
3/ TiO
2composite membrane, by Er
3+: YAlO
3/ TiO
2compound film electrode and graphite electrode fit together, between two electrodes, drip I
2/ I
3-electrolyte, obtains TiO
2solar cell, under three-basic-colour lamp (sending visible ray) irradiates, then measures electric current and voltage.In contrast, one deck individual layer TiO is prepared by same process
2the solar cell of film, measures electric current and voltage.
Measurement result as shown in Figure 3, the simple TiO of one deck
2film TiO
2the electric current of solar cell and voltage are respectively 26 μ A and 0.13V, and one deck mass ratio is the Er of 1:9
3+: YAlO
3/ TiO
2the TiO of composite membrane
2the electric current of solar cell and voltage are respectively 29 μ A and 0.145V, the Er of one deck mass ratio 3:7
3+: YAlO
3/ TiO
2the TiO of composite membrane
2the electric current of solar cell and voltage are respectively 38 μ A and 0.19V.Result shows to add up-conversion luminescent material Er
3+: YAlO
3tiO
2the electric current of solar cell and voltage and simple TiO
2solar cell is compared and is significantly improved, and works as Er
3+: YAlO
3and TiO
2when mass ratio increases, solar cell electric current and voltage improve more than 45%.
2, the Er of different calcination temperature
3+: YAlO
3/ TiO
2composite membrane is used for TiO
2the performance comparison of solar cell
Experiment condition: will 1 layer of Er that mass ratio is 3:7 be coated with
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of composite membrane, respectively at heat treated under 300 ° of C and 500 ° C 60 minutes, naturally cools, obtains 1 layer of Er of different calcination temperature
3+: YAlO
3/ TiO
2composite membrane; Compound film electrode and graphite electrode are fitted together, between two electrodes, drips I
2/ I
3-electrolyte, obtains TiO
2solar cell, under three-basic-colour lamp (sending visible ray) irradiates, measures electric current and voltage.In contrast, the simple TiO of one deck is prepared by same process
2the solar cell of film, measures electric current and voltage.
Measurement result is as shown in Fig. 4-1 and 4-2, and heat treatment temperature is the pure TiO of one deck of 300 ° of C
2the electric current of solar cell and voltage are respectively 20 μ A and 0.1V, and one deck mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage are respectively 27 μ A and 0.135V.Heat treatment temperature is the pure TiO of one deck of 500 ° of C
2the electric current of solar cell and voltage are respectively 26 μ A and 0.13V, and one deck mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage are respectively 38 μ A and 0.19V.Result shows that heat treatment temperature is one deck Er of 500 ° of C
3+: YAlO
3/ TiO
2one deck Er of the electric current of solar cell and voltage and 300 ° of C
3+: YAlO
3/ TiO
2solar cell is compared, and electric current and voltage are significantly improved.Heat treatment temperature is the simple TiO of one deck of 500 ° of C
2solar cell and heat treatment temperature are the simple TiO of one deck of 300 ° of C
2solar cell is compared, and electric current and voltage improve more than 30%.Heat treatment temperature is one deck Er of 500 ° of C
3+: YAlO
3/ TiO
2one deck Er of solar cell and 300 ° of C
3+: YAlO
3/ TiO
2solar cell is compared, and electric current and voltage improve more than 40%.
3, the Er of different calcination time
3+: YAlO
3/ TiO
2composite membrane is used for TiO
2the performance comparison of solar cell
Experiment condition: will 1 layer of Er that mass ratio is 3:7 be coated with
3+: YAlO
3/ TiO
2the electro-conductive glass sheet of composite membrane, respectively at heat treated 30min and 60min under 500 ° of C, naturally cools, obtains 1 layer of Er of different calcination temperature
3+: YAlO
3/ TiO
2composite membrane; Compound film electrode and graphite electrode are fitted together, between two electrodes, drips I
2/ I
3-electrolyte, obtains TiO
2solar cell, under three-basic-colour lamp (sending visible ray) irradiates, measures electric current and voltage.In contrast, the simple TiO of one deck is prepared by same process
2the solar cell of film, measures electric current and voltage.
Measurement result is as shown in Fig. 5-1 and 5-2, and calcination time is the pure TiO of one deck of 30min
2the electric current of solar cell and voltage are respectively 21 μ A and 0.105V, and one deck mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2electric current and voltage be respectively 29 μ A and 0.145V.Calcination time is the pure TiO of one deck of 60min
2the electric current of solar cell and voltage are respectively 26 μ A and 0.13V, and one deck mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2electric current and voltage be respectively 38 μ A and 0.19V.Result shows that calcination time is one deck Er of 30min
3+: YAlO
3/ TiO
2solar cell and the simple TiO of one deck
2solar cell is compared, and electric current and voltage are significantly improved.Calcination time is one deck Er of 60min
3+: YAlO
3/ TiO
2solar cell and the simple TiO of one deck
2solar cell is compared, and electric current and voltage are significantly improved.And calcination time is the simple TiO of one deck of 60min
2the electric current of solar cell and voltage ratio calcination time are the simple TiO of one deck of 30min
2solar cell improves 23%.Calcination time is one deck Er of 60min
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage ratio calcination time are one deck Er of 30min
3+: YAlO
3/ TiO
2solar cell improves more than 31%.
embodiment 3.Er
3+
: YAlO
3
/ TiO
2
composite membrane is at TiO
2
application in solar cell
1, different visible light intensity illumination is on the impact of solar cell properties
Experiment condition: by pure for one deck TiO
2the solar cell of film and one deck mass ratio are the Er of 3:7
3+: YAlO
3/ TiO
2the solar cell of the making of film, respectively under the irradiation of the three-basic-colour lamp of 1 30W and 3 30W, measures electric current and voltage.
Measurement result as shown in Fig. 6-1 and 6-2, the pure TiO of one deck that the three-basic-colour lamp of 1 30W irradiates
2the electric current of solar cell and voltage are respectively 18 μ A and 0.09V, one deck Er
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage be respectively 29 μ A and 0.145V; The pure TiO of one deck of the three-basic-colour lamp irradiation of 3 30W
2the electric current of solar cell and voltage be respectively 26 μ A and 0.13V, one deck Er
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage be respectively 38 μ A and 0.19V.Result shows, one deck Er of the three-basic-colour lamp irradiation of 1 30W
3+: YAlO
3/ TiO
2solar cell and the simple TiO of one deck
2solar cell compare, electric current and voltage are significantly improved; One deck Er of the three-basic-colour lamp irradiation of 3 30W
3+: YAlO
3/ TiO
2solar cell and the simple TiO of one deck
2solar cell compare, electric current and voltage are significantly improved; One deck Er of the three-basic-colour lamp irradiation of 3 30W
3+: YAlO
3/ TiO
2the electric current of solar cell and one deck Er of irradiating of the three-basic-colour lamp of voltage ratio 1 30W
3+: YAlO
3/ TiO
2solar cell improve more than 31%; The simple TiO of one deck of the three-basic-colour lamp irradiation of 3 30W
2the electric current of solar cell and the simple TiO of one deck that irradiates of the three-basic-colour lamp of voltage ratio 1 30W
2electric current and the voltage of solar cell improve 44%.
2, the Er of the different number of plies
3+: YAlO
3/ TiO
2composite membrane is on the impact of solar cell properties
Experiment condition: get the simple TiO of one deck respectively
2film and one deck Er
3+: YAlO
3/ TiO
2composite membrane and two-layer simple TiO
2film and two-layer Er
3+: YAlO
3/ TiO
2composite membrane, makes solar cell, under three-basic-colour lamp (sending visible ray) irradiates, measures electric current and voltage.
Measurement result as shown in Fig. 7-1 and 7-2, the pure TiO of one deck
2the electric current of solar cell and voltage be respectively 26 μ A and 0.13V, one deck Er
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage be respectively 38 μ A and 0.19V, two-layer simple TiO
2the electric current of solar cell and voltage be respectively 29 μ A and 0.145V, two-layer Er
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage be respectively 41 μ A and 0.205V.Result shows, one deck Er
3+: YAlO
3/ TiO
2solar cell and the simple TiO of one deck
2solar cell is compared, and electric current and voltage are significantly improved; Two-layer Er
3+: YAlO
3/ TiO
2solar cell and two-layer simple TiO
2solar cell compare, electric current and voltage are significantly improved; And two-layer simple TiO
2the electric current of solar cell and the simple TiO of voltage ratio one deck
2the electric current of solar cell and voltage improve more than 11%, two-layer Er
3+: YAlO
3/ TiO
2the electric current of solar cell and voltage ratio one deck Er
3+: YAlO
3/ TiO
2solar cell improve more than 8%.
3, the Er of different sequence
3+: YAlO
3/ TiO
2composite membrane is on the impact of solar cell properties
Experiment condition: get two-layer simple TiO respectively
2film, ground floor is Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2, the second layer is pure TiO
2composite membrane and ground floor be pure TiO
2, the second layer is Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2composite membrane, ground floor is near graphite electrode, and the second layer accepts illumination, makes solar cell, under three-basic-colour lamp (sending visible ray) irradiates, measures electric current and voltage.
Measurement result as shown in Figure 8, two-layer simple TiO
2the electric current of film solar cell and voltage are respectively 29 μ A and 0.145V, and ground floor is Er
3+: YAlO
3/ TiO
2film, the second layer are TiO
2the electric current of the solar cell of film and voltage are respectively 34 μ A and 0.17V, and ground floor is TiO
2film, lower floor's (second layer) is Er
3+: YAlO
3/ TiO
2the electric current of the solar cell of film and voltage are respectively 38 μ A and 0.19V.Result shows that certain one deck adds the solar cell of up-conversion luminescent material and two-layer simple TiO
2solar cell is compared, and electric current and voltage are significantly improved.Ground floor is pure TiO
2, the second layer is Er
3+: YAlO
3/ TiO
2solar cell and two-layer simple TiO
2solar cell compare, electric current and voltage improve more than 31%, are Er with ground floor
3+: YAlO
3/ TiO
2, the second layer is pure TiO
2solar cell compare, current/voltage ratio improves more than 12%.
embodiment 4.Er
3+
: Yb
0.2
y
0.79
n
0.1
f
0.1
alO
2.8
/ TiO
2
composite membrane is at TiO
2
application in solar cell
Get simple TiO respectively
2film, Er
3+: YAlO
3with TiO
2mass ratio is the Er of 3:7
3+: YAlO
3/ TiO
2composite membrane and Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2mass ratio is the Er of 3:7
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane.Compound film electrode and graphite electrode are fitted together, between two electrodes, drips I
2/ I
3-electrolyte, obtains three kinds of TiO respectively
2solar cell, under three-basic-colour lamp (sending visible ray) irradiates, measures electric current and voltage.
Result as shown in Figure 9, simple TiO
2the electric current of the solar cell of film and voltage are respectively 26 μ A and 0.13V, Er
3+: YAlO
3/ TiO
2the electric current of the solar cell of composite membrane and voltage are respectively 38 μ A and 0.19V, Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the electric current of the solar cell of composite membrane and voltage are respectively 57 μ A and 0.285V.Result shows to add up-conversion luminescent material Er
3+: YAlO
3tiO
2solar cell and simple TiO
2solar cell is compared, and electric current and voltage are significantly improved, and the Er of the different element that adulterates
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the solar cell of composite membrane and simple TiO
2solar cell and Er
3+: YAlO
3/ TiO
2the solar cell of composite membrane is compared, and electric current and voltage have had further raising, improve more than 34% and 57% respectively.
Claims (3)
1. for a material for solar cell, it is characterized in that: by upper conversion ultra-violet light-emitting material and TiO
2composite membrane for making the electrode material of solar cell; Described upper ultra-violet light-emitting material of changing is into Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8, Er in described composite membrane
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8with TiO
2mass ratio is 1:9 ~ 3:7.
2. the preparation method of a kind of material for solar cell according to claim 1, is characterized in that preparation method is as follows:
1) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of complex sol: get the Er that mass ratio is 1:9 ~ 3:7
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder and TiO
2colloidal sol, stirs, and leaves standstill, obtains target product Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2complex sol;
2) Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2the preparation of composite membrane: electro-conductive glass sheet is dipped vertically into above-mentioned Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2in complex sol, leave standstill after 1.0 minutes, with 0.6cms
-1pull rate by electro-conductive glass sheet at the uniform velocity reposefully from Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2take out dry in complex sol, obtain one deck composite membrane, repeated impregnations, lift, dry, obtain multilayer complex films, heated 30 ~ 60 minutes by composite membrane at 300 ~ 600 DEG C, cooling, obtains Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2composite membrane.
3. the preparation method of a kind of material for solar cell as claimed in claim 2, is characterized in that: described Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8the preparation method of nanometer powder is: by chemical molecular formula Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8/ TiO
2in each element proportioning be converted into Er
2o
3, Yb
2o
3, Y
2o
3, Al (NO
3)
39H
2o, urea and hydrofluoric acid quality than feeding, by Er
2o
3, Yb
2o
3and Y
2o
3be dissolved in red fuming nitric acid (RFNA), then add urea and hydrofluoric acid solution in solution, magnetic agitation also heats until water white transparency, obtains A liquid; Then Al (NO is taken in proportion
3)
39H
2o and citric acid, dissolve with distilled water, the mol ratio of citric acid and rare earth ion is 3:1, obtains B liquid; Room temperature, slowly joins in A liquid by B liquid under stirring, then stirs at 50 ~ 60 DEG C and obtains colloidal sol in 1 ~ 2 hour, heat 32 ~ 38 hours at 80 DEG C, obtain gel, after the gel obtained is heated 50 minutes at 500 DEG C, be warming up to 1100 DEG C of calcinings 120 minutes, obtain Er
3+: Yb
0.2y
0.79n
0.1f
0.1alO
2.8nanometer powder.
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| CN101702377A (en) * | 2009-10-29 | 2010-05-05 | 彩虹集团公司 | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof |
| CN102311734A (en) * | 2011-09-23 | 2012-01-11 | 辽宁大学 | Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof |
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| CN102311734A (en) * | 2011-09-23 | 2012-01-11 | 辽宁大学 | Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof |
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| 可见光响应负载Er3+:YAlO3 / TiO2 –SAC光催化剂的制备及其性能研究;张建宾;《太阳能学报》;20120831;第33卷(第8期);第1295页第2栏第17、18行，第1296页第1栏第1-8行 * |
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