CN102354605A - Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method - Google Patents
Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method Download PDFInfo
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Abstract
The invention provides a method for preparing a doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of a microwave auxiliary reaction supercharge method and belongs to a low-temperature synthesis method of a solar battery photoelectrode. The preparation method comprises the following steps: 1, adding a titaniferous precursor into alcohol, uniformly mixing, then adding an adulterant, stirring, then adding a hydrolysis inhibitor, and slowly dropwise adding deionized water, thus obtaining a mixed solution; 2, heating the mixed solution in a water bath, stirring, refluxing and reacting until the reaction is over, thus obtaining a titaniferous and element-doped colloid; 3, cooling the colloid to room temperature, then transferring the cooled colloid into a high-pressure vessel, adding a decomposition agent and then rapidly sealing the vessel; 4, placing the vessel into a microwave reaction device, rapidly heating, keeping stirring, filtering reaction products, washing with deionized water, and drying, thus obtaining doping-type crystalline titanium dioxide. The method provided by the invention has the advantages that the doping-type crystalline titanium dioxide with grains of about 120nm can be prepared at low temperature; the dispersibility is better; the preparation process time is shorter; and long-term follow-up high-temperature crystallization treatment is not required.
Description
Technical field
The present invention relates to a kind of low-temperature synthetic method of solar cell photoelectric pole, particularly a kind of microwave-assisted reaction supercharge method low temperature prepares doping type crystalline state titanium dioxide photoelectrode.
Background technology
Doping type titanium dioxide is the main material of solar cell photoelectric pole, and the preparation method can be divided into physical deposition method and chemical preparation method.The common depositing temperature of physical deposition method is higher, and the depositing device complex and expensive.The chemical method preparation method mainly contains liquid-phase precipitation method, sol-gal process and hydro thermal method.What liquid-phase precipitation method and Prepared by Sol Gel Method went out is unbodied titanium dioxide, is transformed into the titanium dioxide of crystalline state like need, also will carry out follow-up high-temperature process; Although hydro thermal method can be prepared crystalline state titanium dioxide, reaction temperature is usually more than 150 ℃.If can prepare crystalline state titanium dioxide being no more than under 100 ℃ the cryogenic conditions, help cutting down the consumption of energy on the one hand, can expand its range of application on the other hand, as can on the plastic-substrates of some non-refractories, directly preparing the crystalline state optoelectronic pole.In addition, because the doping type titanium dioxide of low temperature preparation is amorphous state under the normal condition, in order to improve electricity conversion, need be transformed into crystalline state through follow-up high-temperature process, this high-temperature process tends to cause the loss of doped chemical, has reduced the doping effect.
Summary of the invention
The objective of the invention is to provide a kind of microwave-assisted reaction supercharge method low temperature to prepare doping type crystalline state titanium dioxide photoelectrode, solve the problem that under 85～100 ℃ low temperature, is difficult to prepare doping type crystalline state titanium dioxide.
The objective of the invention is to realize like this: the concrete preparation method of doping type crystalline state titanium dioxide photoelectrode is:
One, the presoma that in alcohol, adds titaniferous; Mix the back and add alloy; Fully stir the back and add hydrolysis inhibitor; Slowly drip deionized water then; Make mixed liquor, wherein the mol ratio of the presoma of titaniferous, alcohol, alloy, hydrolysis inhibitor and deionized water is 1:5～100:0.05～5:0.01 ~ 50:0.5 ~ 50;
Two, the mixed liquor with step 1 preparation heats with water-bath, and 40～100 ℃ of bath temperatures keep in the heating process stirring, and reflux, and 0.5～2h afterreaction is accomplished, and makes the colloid of titaniferous and doped chemical;
Three, after the colloid of treating in the step 2 preparation is cooled to room temperature, it is moved in high-pressure-resistant vessel, and add distintegrant, then rapidly with seal of vessel, wherein the mol ratio of the presoma of the titaniferous of adding is 50～1000:1 in distintegrant and the step 1;
Four, the container with good seal in the step 3 is put in the microwave reaction device; Microwave power is 100～800W; Quickly heat up to 85～100 ℃; Insulation 1～4h is to the reaction completion; Keep in the whole process stirring; Product is filtered and use deionized water wash, obtain doping type crystalline state titanium dioxide after the drying.
The presoma of described titaniferous is any in butyl titanate, titanium tetrachloride, the isopropyl titanate.
Described alloy is the water soluble compound that contains in Ag, Zn, Cu, Fe, Al, Co, Sn, Pt, Ru, V, Ta, Nb, Mo, Mn, F, Cl, Br, I, S, B, C, Si, N, the P element any; Or above-mentioned any two combinations; Or the mixture of wantonly three kinds of combinations.
Described hydrolysis inhibitor is divided into acidity, alkalescence and neutral three kinds; Wherein acid inhibitor is any in nitric acid, hydrochloric acid, sulfuric acid, lactic acid, the citric acid; The alkalescence inhibitor is a monoethanolamine; In diethanol amine, triethanolamine, ammoniacal liquor, NaOH, the potassium hydroxide any, neutral inhibitor are any in polyethylene glycol, the PVP.
Described distintegrant is any in hydrogen peroxide solution, ammonium carbonate, carbonic hydroammonium, sodium acid carbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, zinc carbonate, ammonium nitrate, ammonium nilrite, the azodiisobutyronitrile.
Beneficial effect owing to adopted such scheme, in the colloid of titaniferous for preparing and doped chemical, adds distintegrant, utilizes the principle induced crystallization of chemical reaction supercharging; Then, utilize the method for microwave-assisted heating, product degree of crystallinity is improved and minimizing reaction required time, under 85～100 ℃ cryogenic conditions, just can prepare doping type crystalline state titanium dioxide fast.Through in colloid, adding distintegrant; Utilize the principle induced crystallization of chemical reaction supercharging; And the method for utilizing microwave-assisted to heat, make the raising of product degree of crystallinity and reduced the reaction required time, solved the problem that under 85～100 ℃ low temperature, is difficult to prepare doping type crystalline state titanium dioxide.Reached the object of the invention.
Have following advantage:
1, under 85～100 ℃ cryogenic conditions, can prepare doping type crystalline state titanium dioxide, overcome follow-up high-temperature process and caused doped chemical to be prone to the shortcoming that runs off, realize the preparation of the solar cell photoelectric pole of high conversion efficiency.
2, the distintegrant that adds in this invention can be prepared the doping type crystalline state titanium dioxide about the about 12nm of crystal grain effectively, and better dispersed.
3, the preparation process time of this method is short, need not long follow-up high temperature crystallization and handles.The colloid for preparing stage takes 1～2.5h among the present invention, and the microwave-assisted stage takes 1～4h, and whole process only needs 2～6.5h.
Description of drawings
Fig. 1 is the X-ray diffraction of mixing tantalum crystalline state titanium dioxide (XRD) collection of illustrative plates of preparation in the embodiment of the invention 1.
Fig. 2 is x-ray photoelectron power spectrum (XPS) figure that mixes Ta 4f in the tantalum crystalline state titanium dioxide of preparation in the embodiment of the invention 1.
Embodiment
Through embodiment the present invention is detailed below.
Embodiment 1: in 2.30mol ethanol, add the 0.07mol butyl titanate, after mixing, add the 0.013mol ethanol tantalum; Fully stir the back and drip the 0.08mol red fuming nitric acid (RFNA); Slowly drip the 0.20mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 65 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and tantalum behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 2.90mol hydrogen peroxide solution then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 200W, quickly heats up to 95 ℃, and insulation 2.5h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix tantalum crystalline state titanium dioxide granule, dispersed better.
Among Fig. 1; The X-ray diffraction of mixing tantalum crystalline state titanium dioxide (XRD) figure of preparation; Its diffraction maximum shows that products therefrom is anatase phase and rutile mixed crystal attitude titanium dioxide mutually, calculates through Scherrer formula (Scherrer equation), and its crystal average diameter is 12.9nm.Among Fig. 2, x-ray photoelectron power spectrum (XPS) collection of illustrative plates of mixing Ta 4f in the tantalum crystalline state titanium dioxide of preparation shows that tantalum is doped in the titanium dioxide.The assembling of solar cell and the test as follows:
(1) assembling of solar cell: the doping type crystalline state titanium dioxide for preparing with after a certain amount of absolute ethyl alcohol mixes, is fully ground 30min in agate mortar, obtain doping type crystalline state titania slurry.The employing silk screen printing is filmed, and with the dry 10min in 60 ℃ of drying boxes of film elder generation for preparing, at 100 ℃ Muffle furnace low temperature sintering 10min, is incubated 10min then.Then this nano-crystal film is immersed in the acetonitrile that contains the N719 dyestuff and the butanol solution and steep 8h, take out and then uses washing with alcohol, 80 ℃ of dryings can make the doping type crystalline state titanium dioxide photoelectrode of dye sensitization.As work electrode, the electrically-conductive backing plate of platinum plating is as to electrode, with containing 0.5M LiI, 0.05M I with the optoelectronic pole for preparing
2With the acetonitrile solution of 0.5M four tertiary butyl pyridines as liquid electrolyte, be assembled into the DSSC of " sandwich " structure.
(2) Solar cell performance method of testing: the photoelectric properties of battery use a computer control Oriel sunlight analogue system at room temperature test, incident intensity is 100mW/cm
2, illuminating area is 0.25cm
2
Test result shows that open circuit voltage is 0.78V, and short circuit current is 12.74mA/cm
2, fill factor, curve factor is 0.650, photoelectric conversion efficiency is 6.46%.
Embodiment 2: in 1.60mol ethanol, add the 0.05mol butyl titanate, after mixing, add the 0.03mol zinc acetate; Fully stir the back and drip the 0.04mol red fuming nitric acid (RFNA); Slowly drip the 0.10mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 60 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and zinc behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.05mol zinc carbonate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 300W, quickly heats up to 90 ℃, and insulation 2h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix zinc crystalline state titanium dioxide, average grain diameter is 12.0nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.77V, and short circuit current is 11.76mA/cm
2, fill factor, curve factor is 0.647, photoelectric conversion efficiency is 5.86%.
Embodiment 3: in the 3.05mol isopropyl alcohol, add the 0.20mol butyl titanate; After mixing; Add the 0.20mol butter of tin; Fully stir the back and drip the 0.15mol red fuming nitric acid (RFNA); Slowly drip the 0.40mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 70 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and tin behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.04mol ammonium carbonate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 98 ℃, and insulation 2.5h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix tin crystalline state titanium dioxide, average grain diameter is 13.5nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.76V, and short circuit current is 12.71mA/cm
2, fill factor, curve factor is 0.631, photoelectric conversion efficiency is 6.10%.
Embodiment 4: in 1.50mol ethanol, add the 0.15mol titanium tetrachloride; After mixing; Add 0.05mol butter of tin and 0.05mol zinc acetate; Fully stir the back and drip the 0.015mol polyethylene glycol; Slowly drip the 0.20mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 50 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, tin and zinc behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.15mol sodium acid carbonate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 180W, quickly heats up to 85 ℃, and insulation 3.5h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make tin, zinc co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.1nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.72V, and short circuit current is 11.79mA/cm
2, fill factor, curve factor is 0.620, photoelectric conversion efficiency is 5.26%.
Embodiment 5: in 4.50mol ethanol, add the 0.15mol butyl titanate; After mixing; Add 0.010mol Boratex and 0.018mol tetraethoxysilane; Fully stir the back and drip 0.16mol ammoniacal liquor; Slowly drip the 0.21mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 75 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, boron and silicon behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add 0.12mol carbonic hydroammonium then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 97 ℃, and insulation 2h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make boron, silicon coblended crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 12.7nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.71V, and short circuit current is 11.36mA/cm
2, fill factor, curve factor is 0.637, photoelectric conversion efficiency is 5.14%.
Embodiment 6: in the 4.15mol propane diols, add the 0.22mol butyl titanate; After mixing; Add 0.016mol zirconium oxychloride and 0.010mol copper nitrate; Fully stir the back and drip 0.13mol lactic acid; Slowly drip the 0.18mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 80 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, zirconium and copper behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.15mol diammonium hydrogen phosphate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 93 ℃, and insulation 3h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of zirconium, copper codope after 60 ℃ of dryings, average grain diameter is 12.09nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.75V, and short circuit current is 11.09mA/cm
2, fill factor, curve factor is 0.628, photoelectric conversion efficiency is 5.22%.
Embodiment 7: in 5.10mol ethanol, add the 0.16mol butyl titanate; After mixing; Add 0.04mol zinc acetate and 0.15mol ammonium fluoride; Fully stir the back and add the 0.006mol PVP; Slowly drip the 0.17mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 85 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, zinc and fluorine behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.26mol ammonium nilrite then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 700W, quickly heats up to 98 ℃, and insulation 2.5h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make zinc, fluorin-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 13.6nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.75V, and short circuit current is 12.24mA/cm
2, fill factor, curve factor is 0.648, photoelectric conversion efficiency is 5.95%.
Embodiment 8: in 0.04mol ethanol, add the 0.01mol butyl titanate; After mixing; Add 0.005mol manganese sulfate, 0.002mol cobalt nitrate and 0.015mol glucose; Fully stir the back and drip the 0.01mol monoethanolamine; Slowly drip the 0.02mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 65 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, manganese, cobalt and carbon behind the reaction 2h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.05mol hydrogen peroxide solution then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 450W, quickly heats up to 81 ℃, and insulation 3h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make manganese, cobalt, carbon co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.3nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.74V, and short circuit current is 12.18mA/cm2, and fill factor, curve factor is 0.638, and photoelectric conversion efficiency is 5.75%.
Embodiment 9: in 4.80mol ethanol, add the 0.40mol isopropyl titanate; After mixing; Add 0.02mol chloroplatinic acid, 0.02mol ruthenium trichloride, 0.30mol ammonium bromide; Fully stir the back and drip the 0.13mol red fuming nitric acid (RFNA); Slowly drip the 0.30mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 90 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, platinum, ruthenium, bromine behind the reaction 0.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add 0.08mol ammonium nitrate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 650W, quickly heats up to 99 ℃, and insulation 3h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of platinum, ruthenium and bromine codope after 60 ℃ of dryings, average grain diameter is 13.9nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.78V, and short circuit current is 12.63mA/cm
2, fill factor, curve factor is 0.662, photoelectric conversion efficiency is 6.52%.
Embodiment 10: in 0.90mol ethanol, add the 0.025mol butyl titanate; After mixing; Add 0.002mol vanadium trichloride, 0.002mol molybdenum pentachloride and 0.028mol ammonium iodide; Fully stir the back and drip the 0.03mol concentrated sulfuric acid; Slowly drip the 0.05mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 80 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, vanadium, molybdenum and iodine behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.055mol diammonium hydrogen phosphate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 380W, quickly heats up to 92 ℃, and insulation 3.5h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of vanadium, molybdenum and iodine codope after 60 ℃ of dryings, average grain diameter is 12.5nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.69V, and short circuit current is 12.03mA/cm
2, fill factor, curve factor is 0.621, photoelectric conversion efficiency is 5.15%.
Embodiment 11: in 2.30mol ethanol, add the 0.19mol isopropyl titanate; After mixing; Add 0.005mol silver nitrate, 0.002mol ferric nitrate and 0.055mol urea; Fully stir the back and drip the 0.08mol diethanol amine; Slowly drip the 0.16mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 75 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, silver, iron and nitrogen behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.041mol ammonium dihydrogen phosphate then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 550W, quickly heats up to 91 ℃, and insulation 2h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make silver, iron, nitrogen co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.6nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.72V, and short circuit current is 11.21mA/cm
2, fill factor, curve factor is 0.610, photoelectric conversion efficiency is 4.92%.
Embodiment 12: in 0.80mol ethanol, add the 0.03mol butyl titanate; After mixing; Add 0.016mol ethanol niobium, 0.007mol thiocarbamide and 0.005mol ammonium chloride; Fully stir the back and drip the 0.001mol polyethylene glycol; Slowly drip the 0.04mol deionized water after stirring 5min; Keep high-speed stirred in the dropping process, make mixed liquor.The above-mentioned mixed liquor that makes is heated with water-bath, and 90 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, niobium, sulphur and chlorine behind the reaction 2h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, add the 0.02mol azodiisobutyronitrile then, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 600W, quickly heats up to 92 ℃, and insulation 3h accomplishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make niobium, sulphur, chlorine co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 12.8nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows that open circuit voltage is 0.75V, and short circuit current is 11.27mA/cm
2, fill factor, curve factor is 0.667, photoelectric conversion efficiency is 5.64%.
Claims (5)
1. a microwave-assisted reaction supercharge method low temperature prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: the concrete preparation method of doping type crystalline state titanium dioxide photoelectrode is:
One, the presoma that in alcohol, adds titaniferous; Mix the back and add alloy; Fully stir the back and add hydrolysis inhibitor; Slowly drip deionized water then; Make mixed liquor, wherein the mol ratio of the presoma of titaniferous, alcohol, alloy, hydrolysis inhibitor and deionized water is 1:5～100:0.05～5:0.01 ~ 50:0.5 ~ 50;
Two, the mixed liquor with step 1 preparation heats with water-bath, and 40～100 ℃ of bath temperatures keep in the heating process stirring, and reflux, and 0.5～2h afterreaction is accomplished, and makes the colloid of titaniferous and doped chemical;
Three, after the colloid of treating in the step 2 preparation is cooled to room temperature, it is moved in high-pressure-resistant vessel, and add distintegrant, then rapidly with seal of vessel, wherein the mol ratio of the presoma of the titaniferous of adding is 50～1000:1 in distintegrant and the step 1;
Four, the container with good seal in the step 3 is put in the microwave reaction device; Microwave power is 100～800W; Quickly heat up to 85～100 ℃; Insulation 1～4h is to the reaction completion; Keep in the whole process stirring; Product is filtered and use deionized water wash, obtain doping type crystalline state titanium dioxide after the drying.
2. microwave-assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: the presoma of described titaniferous is any in butyl titanate, titanium tetrachloride, the isopropyl titanate.
3. microwave-assisted according to claim 1 reaction supercharge method low temperature prepares doping type crystalline state titanium dioxide photoelectrode, it is characterized in that: described alloy is the water soluble compound that contains in Ag, Zn, Cu, Fe, Al, Co, Sn, Pt, Ru, V, Ta, Nb, Mo, Mn, F, Cl, Br, I, S, B, C, Si, N, the P element any; Or above-mentioned any two combinations; Or the mixture of wantonly three kinds of combinations.
4. microwave-assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode; It is characterized in that: described hydrolysis inhibitor is divided into acidity, alkalescence and neutral three kinds; Wherein acid inhibitor is any in nitric acid, hydrochloric acid, sulfuric acid, lactic acid, the citric acid; The alkalescence inhibitor is a monoethanolamine; In diethanol amine, triethanolamine, ammoniacal liquor, NaOH, the potassium hydroxide any, neutral inhibitor are any in polyethylene glycol, the PVP.
5. microwave-assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: described distintegrant is any in hydrogen peroxide solution, ammonium carbonate, carbonic hydroammonium, sodium acid carbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, zinc carbonate, ammonium nitrate, ammonium nilrite, the azodiisobutyronitrile.
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| CN105895807A (en) * | 2016-05-06 | 2016-08-24 | 郑州大学 | Preparation method of TiO2-dopted film |
| CN106356523A (en) * | 2016-10-13 | 2017-01-25 | 华中科技大学 | Preparation method of titanium dioxide sodium-ion battery cathode material and product thereof |
| CN110605096A (en) * | 2019-09-23 | 2019-12-24 | 浙江省家具与五金研究所 | Preparation method and application of carbon-doped rutile particles |
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| CN113430858A (en) * | 2021-07-21 | 2021-09-24 | 杭州众材科技股份有限公司 | Self-cleaning modification method for paper surface |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895807A (en) * | 2016-05-06 | 2016-08-24 | 郑州大学 | Preparation method of TiO2-dopted film |
| CN105895807B (en) * | 2016-05-06 | 2018-11-16 | 郑州大学 | A kind of doping TiO2The preparation method of film |
| CN106356523A (en) * | 2016-10-13 | 2017-01-25 | 华中科技大学 | Preparation method of titanium dioxide sodium-ion battery cathode material and product thereof |
| CN106356523B (en) * | 2016-10-13 | 2019-05-31 | 华中科技大学 | A kind of preparation method and products thereof of titanium dioxide anode material of lithium-ion battery |
| CN112397625A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN110605096A (en) * | 2019-09-23 | 2019-12-24 | 浙江省家具与五金研究所 | Preparation method and application of carbon-doped rutile particles |
| CN110605096B (en) * | 2019-09-23 | 2022-04-26 | 浙江省家具与五金研究所 | Preparation method and application of carbon-doped rutile particles |
| CN113430858A (en) * | 2021-07-21 | 2021-09-24 | 杭州众材科技股份有限公司 | Self-cleaning modification method for paper surface |
| CN113430858B (en) * | 2021-07-21 | 2022-03-15 | 杭州众材科技股份有限公司 | Self-cleaning modification method for paper surface |
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