CN109166732B - Zn-doped TiO2Preparation method of nanocrystalline photoanode - Google Patents
Zn-doped TiO2Preparation method of nanocrystalline photoanode Download PDFInfo
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Abstract
The invention discloses Zn-doped TiO2The preparation method of the nanocrystalline photoanode comprises the following specific operation steps: dissolving metal Ti powder and Zn powder with a set molar ratio in a hydrochloric acid solution to prepare a Ti ion and Zn ion solution and prepare Zn-doped TiO2Precursor and preparation of Zn-doped TiO2Nanocrystalline preparation of Zn-doped TiO2Nanocrystalline slurry and preparation of quantum dot sensitized Zn-doped TiO2A nanocrystalline photoanode. The invention has simple process, low cost, scale production and good repeatability, and the two most key technologies in the whole process are as follows: dissolving metal Ti and Zn in acid to prepare precursor ions; obtaining Zn-doped TiO with good dispersibility2And (5) annealing the nanocrystalline. The photoanode prepared by the method reduces TiO by doping Zn2The band gap of the material improves the electron transmission characteristic, thereby improving the photoelectric conversion performance of the cell.
Description
Technical Field
The invention belongs to the technical field of solar cell photo-anode preparation methods, and particularly relates to Zn-doped TiO2A method for preparing a nanocrystalline photoanode.
Background
In recent years, with the increasing demand of people for energy and the continuous decrease of petrochemical fuel reserves, the search for a new green alternative energy with rich sources has become one of the important issues in current scientific research. Solar energy is increasingly receiving worldwide attention as an inexhaustible natural energy source, and particularly, the research of solar cells for directly converting solar energy into electric energy has become a hot spot of current research.
Sensitized solar cells are of great interest because of their low cost, environmental friendliness, simple fabrication process, and acceptable conversion efficiency. Over the last two decades, many research efforts have been undertaken to enhance cell efficiency, such as semiconductor photoanodes, sensitizers (dyes or quantum dots), electrolytes and improvements to the electrodes. In the sensitized solar cell structure, a semiconductor photo-anode is one of the important components of the cell, and the main functions of the semiconductor photo-anode are to adsorb a sensitizer and transmit photo-generated electrons. Various metal oxides have been applied to photoanodes, such as TiO2、 ZnO、SnO2And ZrO2. Among these metal oxides, nano TiO2Has the advantages of good chemical stability, low cost, strong charge transmission capability and the like, and is a good candidate material. The high electron transport capability of the photoanode material is one of the important concerns for the performance of the battery. It is well known that metal ion doping is the conditioning of TiO2An important method of material properties (fermi level, bandgap and conductivity). Zn doped TiO2Is an n-type doped material, whereinThe excess negative charge facilitates electron transport, and Zn doping also modulates TiO2The optical band gap and fermi level of the material. Currently, Zn is doped with TiO2There have been some reports of studies for photoanodes in sensitized solar cells [ k. — p.wang, h.s.teng, phys.chem.chem.phys.,2009,11: 9489; G.Zhu, Z.Cheng, T.Lv, et al Nanoscale,2010,2, 1229-1232; M-C.Wu, S-H.Chan, M-H.Jao, et al&Solar Cells,2016,157:447–453；J.Cao,Y.Zhu,X.Yang,et al.Solar Energy Materials&Solar Cells,2016,157:814–819.]Summarizing the analysis, the literature shows that Zn doped TiO2The preparation of the photo-anode material adopts titanium tetrachloride, titanium isopropoxide and tetrabutyl titanate as Ti4+Source and soluble zinc salts (zinc acetate, zinc nitrate, zinc chloride, zinc sulfate) as Zn2+Source although Zn2+The cost of the source is relatively low, but Ti4+The cost of the source is relatively high and the Ti is4+The source is easy to hydrolyze in the air and is not easy to control; on the other hand, the adopted sol-gel method is easy to agglomerate in the annealing process.
Disclosure of Invention
The invention aims to provide Zn-doped TiO2The preparation method of the nanocrystalline photoanode solves the problem of preparing Zn-doped TiO by the existing sol-gel method2The cost of raw materials in the nano material is relatively high, and the nano crystal is easy to agglomerate and has poor dispersibility in the crystallization annealing process.
The technical scheme adopted by the invention is that Zn-doped TiO2The preparation method of the nanocrystalline photoanode comprises the following specific operation steps:
step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning Ti powder by using deionized water and ethanol respectively, ultrasonically cleaning Zn powder by using deionized water and ethanol respectively, and then drying the cleaned Ti powder and Zn powder in a drying box respectively until the deionized water and the ethanol are completely evaporated;
step 1.2: weighing Zn powder and Ti powder treated in the step 1.1 according to a molar ratio of 0-0.5:1, and mixing to obtain mixed metal powder;
step 1.3: dispersing mixed metal powder in HCl solution with mass concentration of 20-30%, standing for 5-7 days at room temperature until no bubbles are generated, obtaining acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 5-10 times with deionized water to obtain diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L alkaline solution, adding the alkaline solution into the diluted solution under magnetic stirring, wherein the volume ratio of the alkaline solution to the diluted solution is 2-2.5:1, and stopping adding and stirring until no blue precipitate is generated to obtain blue emulsion;
step 2.2: standing the blue emulsion for 5-7 days to generate white precipitate;
step 2.3: centrifugally cleaning the white precipitate with deionized water until the pH of the cleaned deionized water is reduced to 6.5-7.5 to obtain Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing Zn-doped TiO2Precursor, doping Zn with TiO2Uniformly dispersing the precursor into absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, and dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: adding the mixed solution A into the ethanol solution of the precursor in the step 3.1 under magnetic stirring, stirring for 3-4 days to obtain a mixed solution B, placing the mixed solution B in a water bath at 60-70 ℃, stirring until absolute ethanol is completely volatilized, transferring the remainder into a crucible, annealing in a muffle furnace at 400-500 ℃ for 4-6h, naturally cooling to room temperature, and finally grinding the powder obtained by annealing for 3-4h to obtain Zn-doped TiO2A nanocrystal;
and 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, performing ultrasonic treatment for 8-10 times at intervals, stirring, and addingAdding terpineol, and continuing to perform ultrasonic treatment and stirring for 2-4 times at intervals to obtain mixed slurry;
step 4.2: weighing ethyl cellulose again, dissolving the ethyl cellulose in absolute ethyl alcohol to obtain ethyl cellulose ethanol solution, adding the ethyl cellulose ethanol solution into the mixed slurry obtained in the step 4.1, performing ultrasonic treatment and stirring for 2-4 times, stirring for 6-8 days, and stirring in a water bath at the temperature of 60-80 ℃ until the absolute ethyl alcohol is completely volatilized to obtain Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO on FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 8-10min, heating in a drying oven at 60-80 deg.C for 5-10min after the slurry flow is balanced, and coating the above Zn-doped TiO2The steps of nanocrystalline slurry are cycled for 4 times, and finally the coated Zn-doped TiO is added2Putting the nanocrystalline slurry film into a muffle furnace, heating from room temperature to 450 ℃ at the speed of 3 ℃/min, and annealing for 30-35min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
The present invention is also characterized in that,
step 1.1 ultrasonic cleaning with deionized water and ethanol for 3-4 times.
In step 1.3, 90ml of HCl solution with the mixture ratio concentration of 20-30% is mixed with 3-4g of mixed metal powder.
The alkaline solution in step 2.1 is one of potassium hydroxide, sodium hydroxide or ammonia water.
Step 3.1 milky Zn-doped TiO per 3g2The precursor is prepared by 100ml of absolute ethyl alcohol.
Step 3.1 doping Zn with TiO2The precursor is dispersed into absolute ethyl alcohol by an ultrasonic stirring mode.
In step 3.2, 100ml of absolute ethyl alcohol is prepared by every 1.5g of ethyl cellulose and 12g of terpineol.
Step 4.1 Zn-doped TiO 1g per2The proportion of the nano-crystal is 20ml of absolute ethyl alcohol; 4.1, the interval ultrasound and stirring are firstly ultrasound for 1 hour and then stirring for 2 hours; step 4.1 terpineol and Zn doped TiO2The mass ratio of the nano-crystals is 1: 4.
In the step 4.2, 20ml of absolute ethyl alcohol is matched with every 0.5g of ethyl cellulose, and in the step 4.2, the ultrasonic treatment and the stirring are firstly carried out for 1 hour and then are carried out for 1 hour.
The invention has the beneficial effects that: the Zn-doped TiO of the invention2The preparation process of the nanocrystalline photoanode is simple, low in cost, large-scale and good in repeatability, and the most key technology in the whole process is to prepare precursor ions of metal Ti and Zn in an acid solution and obtain Zn-doped TiO2And (5) annealing the nanocrystalline. The photoanode prepared by the method reduces TiO by doping Zn2The band gap of the material can enhance the separation of photogenerated electron-hole pairs at the material interface, and the excessive negative charge is provided by n-type Zn doping, so that the TiO can be enhanced2The electron transmission capability of the material is improved, so that the photoelectric conversion performance of the battery is improved.
Drawings
FIG. 1 shows a Zn-doped TiO compound of the present invention2A low magnification SEM image of the nanocrystalline porous membrane;
FIG. 2 shows a Zn-doped TiO compound of the present invention2High magnification SEM image of nanocrystalline porous membrane;
FIG. 3 shows a Zn-doped TiO compound of the present invention2TEM images of nanocrystalline porous films;
FIG. 4 shows a Zn-doped TiO compound of the present invention2Electron diffraction patterns of selected areas of the nanocrystalline porous film;
FIG. 5 shows different concentrations of Zn-doped TiO according to the invention2The absorption spectrum of the nanocrystalline porous film of (1);
FIG. 6 shows different concentrations of Zn-doped TiO according to the present invention2The photoluminescence spectrum of the nanocrystalline porous film of (1);
FIG. 7 shows different concentrations of Zn-doped TiO according to the present invention2The cell I-V curve of the nanocrystalline photoanode of (a).
Detailed Description
The invention provides Zn-doped TiO2The preparation method of the nanocrystalline photoanode comprises the following operation steps:
step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning metal Ti powder for 3-4 times by using deionized water and ethanol, ultrasonically cleaning Zn powder for 3-4 times by using deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying box until the deionized water and the ethanol are completely evaporated;
step 1.2: according to the molar ratio of 0-0.5:1 weighing Zn powder and Ti treated in the step 1.1, and mixing the Zn powder and the Ti to obtain mixed metal powder;
step 1.3: dispersing the mixed metal powder in an HCl solution with the mass concentration of 20-30%, wherein 90ml of HCl solution is needed for every 3-4g of mixed metal powder, standing for 5-7 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 5-10 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L alkaline solution, slowly adding the alkaline solution into the diluted solution under magnetic stirring, wherein the volume ratio of the alkaline solution to the diluted solution is 2-2.5:1, and stopping stirring until no blue precipitate is generated to obtain blue emulsion;
the alkaline solution in step 2.1 is one of potassium hydroxide, sodium hydroxide or ammonia water.
Step 2.2: standing the blue emulsion for 5-7 days until the emulsion does not generate bubbles and is completely whitened to generate white precipitates;
step 2.3: centrifugally cleaning the white precipitate by using deionized water until the pH is reduced to 6.5-7.5 to obtain milky Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing Zn-doped TiO2Precursor, the milky Zn is doped with TiO2The precursor is ultrasonically stirred and uniformly dispersed to absolute ethyl alcoholIn each case 3g of milky Zn-doped TiO2The precursor is matched with 100ml of absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol, and matching each 1.5g of the ethyl cellulose and each 12g of the terpineol with 100ml of the absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: adding the mixed solution A into the ethanol solution of the precursor in the step 3.1 under magnetic stirring, stirring for 3-4 days to obtain a mixed solution B, placing the mixed solution B in a water bath at 60-70 ℃, stirring until absolute ethanol is completely volatilized, transferring the remainder into a crucible, annealing in a muffle furnace at 400-500 ℃ for 4-6h, naturally cooling to room temperature, and finally grinding the powder obtained by annealing for 3-4h to obtain Zn-doped TiO2A nanocrystal;
and 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, and doping TiO into every 1g of Zn2The nanocrystalline is prepared by 20ml of absolute ethyl alcohol, and after 8-10 times of interval ultrasonic treatment and stirring, the interval ultrasonic treatment and stirring are firstly performed for 1 hour and then performed for 2 hours; then adding terpineol, wherein the terpineol and the Zn-doped TiO2Continuously carrying out ultrasonic treatment and stirring for 2-4 times at intervals to obtain mixed slurry, wherein the mass ratio of the nanocrystalline is 1: 4;
step 4.2: weighing ethyl cellulose again and dissolving the ethyl cellulose in absolute ethyl alcohol, wherein each 0.5g of the ethyl cellulose is matched with 20ml of absolute ethyl alcohol, carrying out ultrasonic treatment and stirring for 2-4 times, wherein the ultrasonic treatment and stirring are carried out for 1 hour and then 2 hours, and after stirring for 6-8 days, continuously stirring in a water bath at the temperature of 60-80 ℃ until the absolute ethyl alcohol is completely volatilized, so as to obtain the Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO conductive glass on the FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 8-10min, and adding the slurry after the slurry flow is balancedHeating in oven at 60-80 deg.C for 5-10min to coat the Zn-doped TiO2The step of the nanocrystalline slurry is circulated for 4 times, the coated wet film is placed into a muffle furnace, and annealing is carried out for 30-35min from room temperature to 450 ℃ at the speed of 3 ℃/min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
Regarding the CdS/CdSe/ZnS quantum dot deposition, which is a common method, (CdS quantum dot deposition: preparing Cd with the concentration of 0.1M respectively2+(Cd(NO3)2Or Cd (OAc)2) And S2-(Na2S) 50ml of solution, Zn was doped with TiO by SILAR method2The porous membrane is alternately immersed into the two prepared solutions, and CdS quantum dots are generated on the surface of the porous membrane through reaction. CdSe quantum dot deposition: with KBH4Reduction of SeO in deionized Water as reducing agent2Or Se powder to obtain Se2-0.05mol/L solution (inert gas is introduced for the whole process), and Cd (NO)3)2(or Cd (OAc)2) Cd dissolved in deionized water to prepare Cd with concentration of 0.05mol/L2+Solution of Zn doped TiO deposited CdS quantum dot by SILAR method (continuous ion layer adsorption and reaction)2The porous membrane is alternately immersed into the two solutions prepared above, and CdSe quantum dots are generated on the surface of the porous membrane through reaction. ZnS quantum dot deposition: zn with the concentration of 0.1M respectively is prepared2+(Zn(NO3)2Or Zn (OAc)2) And S2-(Na2S) 50ml of solution, and depositing Zn doped TiO of CdS/CdSe quantum dots by using SILAR method2The porous membrane is alternately immersed into the two solutions prepared above, and a ZnS passivation layer is generated on the surface of the porous membrane through reaction.
The preparation method of the invention is also suitable for preparing other metal oxides soluble in acid and doped oxide nanoparticles, such as Al and Cu doped TiO2Nanoparticles, Al, Cu doped ZnO nanoparticles, SnO2With doped SnO2The nano-particles can be used for preparing a nano-crystal photo-anode.
Description of the preparation method: hair brushDissolving high-purity metal Ti powder and Zn powder in HCl solution at room temperature to obtain Ti3+With Zn2+Ion, using a base (OH)-) Solution injection into Ti3+With Zn2+Reacting in ionic solution to obtain Ti (OH)3·Zn(OH)2Blue precipitate, and oxidizing the blue precipitate completely to Ti (OH) in air4·Zn(OH)2White precipitate, using ethyl cellulose and terpineol as annealing auxiliary agent, mixing it with Ti (OH)4·Zn(OH)2Uniformly mixing, annealing to obtain Zn-doped TiO with uniform size and good dispersibility2Nanocrystalline and preparation of Zn-doped TiO suitable for screen printing2Preparing porous Zn-doped TiO slurry by adopting screen printing technology and annealing process2A nanocrystalline photoanode. Zn-doped TiO of the invention2The nanocrystalline photoanode has the advantages of simple preparation process, low cost, large-scale production and good repeatability, and the most key technology in the whole process is to prepare precursor ions of metal Ti and Zn in an acid solution and obtain Zn-doped TiO2And (5) annealing the nanocrystalline. The photoanode prepared by the method reduces TiO by doping Zn2The band gap of the material can enhance the separation of photogenerated electron-hole pairs at the material interface, and the excessive negative charge is provided by n-type Zn doping, so that the TiO can be enhanced2The electron transmission capability of the material is improved, so that the photoelectric conversion performance of the battery is improved.
The present invention will be described in detail with reference to specific examples.
Example 1
Step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning metal Ti powder for 3 times by using deionized water and ethanol, ultrasonically cleaning Zn powder for 3 times by using deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying box until the deionized water and the ethanol are completely evaporated;
step 1.2: according to a molar ratio of 0: 10 weighing the Zn powder and the Ti dried in the step 1.1, and mixing the Zn powder and the Ti to obtain mixed metal powder;
step 1.3: dispersing the metal mixed powder in an HCl solution with the mass concentration of 20%, wherein 90ml of HCl solution is needed for every 3g of metal mixed powder, standing for 5-7 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 5 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L potassium hydroxide, slowly adding the potassium hydroxide into the diluted solution under magnetic stirring, wherein the volume ratio of the potassium hydroxide to the diluted solution is 2:1, and stopping stirring until no blue precipitate is generated to obtain a blue emulsion;
step 2.2: standing the blue emulsion for 5 days until the emulsion does not generate bubbles and is completely whitened to generate white precipitates;
step 2.3: centrifugally cleaning the white precipitate by using deionized water until the pH is reduced to 6.5 to obtain milky Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing milky Zn-doped TiO2Precursor, the milky Zn is doped with TiO2The precursor is evenly dispersed into absolute ethyl alcohol by ultrasonic stirring, and every 3g of milky Zn is doped with TiO2The precursor is matched with 100ml of absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol, and matching each 1.5g of the ethyl cellulose and each 12g of the terpineol with 100ml of the absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: gradually adding the mixed solution A into the precursor ethanol solution under magnetic stirring, stirring for 3 days to obtain a mixed solution B, placing the mixed solution B in a water bath at 60 ℃ to stir until absolute ethanol is completely volatilized, then transferring the remainder into a ceramic crucible, annealing in a muffle furnace at 400 ℃ for 6 hours, naturally cooling to room temperature, taking out to obtain dry powder, and finally grinding the dry powder for 3 hours to obtain Zn-doped TiO2A nanocrystal;
and 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, and doping TiO into every 1g of Zn2The nanocrystalline is prepared by 20ml of absolute ethyl alcohol, and after 8 times of interval ultrasonic treatment and stirring, the interval ultrasonic treatment and stirring are firstly performed for 1 hour and then performed for 2 hours; then adding terpineol, wherein the terpineol and the Zn-doped TiO2Continuously carrying out ultrasonic treatment and stirring for 2 times at intervals to obtain mixed slurry, wherein the mass ratio of the nanocrystalline is 1: 4;
step 4.2: weighing ethyl cellulose again and dissolving the ethyl cellulose in absolute ethyl alcohol, wherein each 0.5g of the ethyl cellulose is matched with 20ml of absolute ethyl alcohol, carrying out ultrasonic treatment and stirring for 2 times, wherein the ultrasonic treatment and stirring are carried out for 1 hour and then 2 hours, and after stirring for 6 days, continuously stirring in a water bath at 60 ℃ until the absolute ethyl alcohol is completely volatilized to obtain Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO conductive glass on the FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 8min, heating in a drying oven at 60 deg.C for 5min after the slurry flow is balanced, and coating the above Zn-doped TiO2The step of the nanocrystalline slurry is circulated for 4 times, the coated wet film is placed into a muffle furnace, and annealing is carried out for 30min from room temperature to 450 ℃ at the speed of 3 ℃/min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
Example 2
Step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning metal Ti powder for 4 times by using deionized water and ethanol, ultrasonically cleaning Zn powder for 4 times by using deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying box until the deionized water and the ethanol are completely evaporated;
step 1.2: weighing the Zn powder and the Ti dried in the step 1.1 according to a molar ratio of 1:9, and mixing the Zn powder and the Ti to obtain mixed metal powder;
step 1.3: dispersing the metal mixed powder in an HCl solution with the mass concentration of 30%, wherein 90ml of HCl solution is needed for every 4g of metal mixed powder, standing for 7 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 10 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L sodium hydroxide, slowly adding the sodium hydroxide into the diluted solution under magnetic stirring, wherein the volume ratio of the sodium hydroxide to the diluted solution is 2.2:1, and stopping stirring until no blue precipitate is generated to obtain a blue emulsion;
step 2.2: standing the blue emulsion for 7 days until the emulsion does not generate bubbles and is completely whitened to generate white precipitates;
step 2.3: centrifugally cleaning the white precipitate by using deionized water until the pH is reduced to 7.5 to obtain milky Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing milky Zn-doped TiO2Precursor, the milky Zn is doped with TiO2The precursor is evenly dispersed into absolute ethyl alcohol by ultrasonic stirring, and every 3g of milky Zn is doped with TiO2The precursor is matched with 100ml of absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol, and matching each 1.5g of the ethyl cellulose and each 12g of the terpineol with 100ml of the absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: gradually adding the mixed solution A into the precursor ethanol solution under magnetic stirring, stirring for 4 days to obtain a mixed solution B, placing the mixed solution B in a water bath at 70 ℃ for stirring until the absolute ethanol is completely volatilized, and then transferring the remainder into a ceramic crucibleAnnealing in a muffle furnace at 500 ℃ for 4h, naturally cooling to room temperature, taking out to obtain dry powder, and finally grinding the dry powder for 4h to obtain Zn-doped TiO2And (4) nanocrystals.
And 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, and doping TiO into every 1g of Zn2The nanocrystalline is prepared by 20ml of absolute ethyl alcohol, and after 10 times of interval ultrasonic treatment and stirring, the interval ultrasonic treatment and stirring are firstly performed for 1 hour and then performed for 2 hours; then adding terpineol, wherein the terpineol and the Zn-doped TiO2Continuously carrying out ultrasonic treatment and stirring for 4 times at intervals to obtain mixed slurry, wherein the mass ratio of the nanocrystalline is 1: 4;
step 4.2: weighing ethyl cellulose again and dissolving the ethyl cellulose in absolute ethyl alcohol, wherein each 0.5g of the ethyl cellulose is matched with 20ml of absolute ethyl alcohol, carrying out ultrasonic treatment and stirring for 4 times, wherein the ultrasonic treatment and stirring are carried out for 1 hour and then 2 hours, and after stirring for 8 days, continuously stirring in a water bath at the temperature of 80 ℃ until the absolute ethyl alcohol is completely volatilized to obtain the Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO conductive glass on the FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 10min, heating in a drying oven at 80 deg.C for 10min after the slurry flow is balanced, and coating the above coating with Zn-doped TiO2The step of the nanocrystalline slurry is circulated for 4 times, the coated wet film is placed into a muffle furnace, and annealing is carried out for 35min from room temperature to 450 ℃ at the speed of 3 ℃/min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
Example 3
Step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning metal Ti powder for 3 times by using deionized water and ethanol, ultrasonically cleaning Zn powder for 4 times by using deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying box until the deionized water and the ethanol are completely evaporated;
step 1.2: weighing the Zn powder and the Ti dried in the step 1.1 according to a molar ratio of 3:7, and mixing the Zn powder and the Ti to obtain mixed metal powder;
step 1.3: dispersing the metal mixed powder in an HCl solution with the mass concentration of 25%, wherein 90ml of the HCl solution is required for every 3.5g of the metal mixed powder, standing for 6 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 8 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L ammonia water, slowly adding the sodium hydroxide into the diluted solution under magnetic stirring, wherein the volume ratio of the sodium hydroxide to the diluted solution is 2.5:1, and stopping stirring until no blue precipitate is generated to obtain blue emulsion;
step 2.2: standing the blue emulsion for 6 days until the emulsion does not generate bubbles and is completely whitened to generate white precipitates;
step 2.3: centrifugally cleaning the white precipitate by using deionized water until the pH is reduced to 7 to obtain milky Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing Zn-doped TiO2Precursor, doping the Zn with TiO2The precursor is evenly dispersed into absolute ethyl alcohol by ultrasonic stirring, and every 3g of milky Zn is doped with TiO2The precursor is matched with 100ml of absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol, and matching each 1.5g of the ethyl cellulose and each 12g of the terpineol with 100ml of the absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: gradually mixing the mixture under magnetic stirringAdding the solution A into the precursor ethanol solution, stirring for 3 days to obtain a mixed solution B, placing the mixed solution B in a water bath at 65 ℃ for stirring until absolute ethanol is completely volatilized, then transferring the remainder into a ceramic crucible, annealing for 5 hours in a muffle furnace at 450 ℃, naturally cooling to room temperature, taking out to obtain dry powder, and finally grinding the dry powder for 3.5 hours to obtain Zn-doped TiO2And (4) nanocrystals.
And 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, and doping TiO into every 1g of Zn2The nanocrystalline is prepared by 20ml of absolute ethyl alcohol, and after 9 times of interval ultrasonic treatment and stirring, the interval ultrasonic treatment and stirring are firstly performed for 1 hour and then performed for 2 hours; then adding terpineol, wherein the terpineol and the Zn-doped TiO2Continuously carrying out ultrasonic treatment and stirring for 3 times at intervals to obtain mixed slurry, wherein the mass ratio of the nanocrystalline is 1: 4;
step 4.2: weighing ethyl cellulose again and dissolving the ethyl cellulose in absolute ethyl alcohol, wherein each 0.5g of the ethyl cellulose is matched with 20ml of absolute ethyl alcohol, carrying out ultrasonic treatment and stirring for 3 times, wherein the ultrasonic treatment and stirring are carried out for 1 hour and then 2 hours, and after stirring for 7 days, continuously stirring in a water bath at 70 ℃ until the absolute ethyl alcohol is completely volatilized to obtain Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO conductive glass on the FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 9min, heating in a 70 deg.C oven for 8min after the slurry flow is balanced, and coating the above coating with Zn-doped TiO2The step of the nanocrystalline slurry is circulated for 4 times, the coated wet film is placed into a muffle furnace, and the temperature is raised from room temperature to 450 ℃ at the speed of 3 ℃/min for annealing for 32min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2CdS/CdSe/ZnS quantum dots deposited on the surface of the nano-crystalline porous membrane to obtain the nano-crystalline porous membrane for the solar cellA photo-anode of the cell.
Example 4
Step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning metal Ti powder for 4 times by using deionized water and ethanol, ultrasonically cleaning Zn powder for 3 times by using deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying box until the deionized water and the ethanol are completely evaporated;
step 1.2: weighing the Zn powder and the Ti treated in the step 1.1 according to a molar ratio of 1:1, and mixing the Zn powder and the Ti to obtain mixed metal powder;
step 1.3: dispersing the metal mixed powder in an HCl solution with the mass concentration of 20%, wherein 90ml of HCl solution is needed for every 4g of metal mixed powder, standing for 5 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 6 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L potassium hydroxide, slowly adding the potassium hydroxide into the diluted solution under magnetic stirring, wherein the volume ratio of the potassium hydroxide to the diluted solution is 2:1, and stopping stirring until no blue precipitate is generated to obtain a blue emulsion;
step 2.2: standing the blue emulsion for 7 days until the emulsion does not generate bubbles and is completely whitened to generate white precipitates;
step 2.3: centrifugally cleaning the white precipitate by using deionized water until the pH is reduced to 7 to obtain milky Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing Zn-doped TiO2Precursor, doping the Zn with TiO2The precursor is evenly dispersed into absolute ethyl alcohol by stirring, and every 3g of milky Zn is doped with TiO2The precursor is matched with 100ml of absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol, and matching each 1.5g of the ethyl cellulose and each 12g of the terpineol with 100ml of the absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: gradually adding the mixed solution A into the precursor ethanol solution under magnetic stirring, stirring for 3 days to obtain a mixed solution B, stirring the mixed solution B in a 70 ℃ water bath until absolute ethanol is completely volatilized, then transferring the remainder into a ceramic crucible, annealing in a 500 ℃ muffle furnace for 5 hours, naturally cooling to room temperature, taking out to obtain dry powder, and finally grinding the dry powder for 3 hours to obtain Zn-doped TiO2And (4) nanocrystals.
And 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, and doping TiO into every 1g of Zn2The nanocrystalline is prepared by 20ml of absolute ethyl alcohol, and after 10 times of interval ultrasonic treatment and stirring, the interval ultrasonic treatment and stirring are firstly performed for 1 hour and then performed for 2 hours; then adding terpineol, wherein the terpineol and the Zn-doped TiO2Continuously carrying out ultrasonic treatment and stirring for 3 times at intervals to obtain mixed slurry, wherein the mass ratio of the nanocrystalline is 1: 4;
step 4.2: weighing ethyl cellulose again and dissolving the ethyl cellulose in absolute ethyl alcohol, wherein each 0.5g of the ethyl cellulose is matched with 20ml of absolute ethyl alcohol, carrying out ultrasonic treatment and stirring for 4 times, wherein the ultrasonic treatment and stirring are carried out for 1 hour and then 2 hours, and after stirring for 7 days, continuously stirring in a water bath at 70 ℃ until the absolute ethyl alcohol is completely volatilized to obtain Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO conductive glass on the FTO conductive glass of the compact layer by adopting a screen printing technology2Standing the nanocrystalline slurry in air for 8min, heating in a drying oven at 60 deg.C for 10min after the slurry flow is balanced, and coating the above coating with Zn-doped TiO2The step of the nanocrystalline slurry is circulated for 4 times, then the coated wet film is put into a muffle furnace, and the temperature is raised from room temperature to 450 ℃ at the speed of 3 ℃/min for annealing for 35min to obtain Zn doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
As can be seen from the low-magnification SEM image shown in FIG. 1, Zn-doped TiO is present in a large area2The surface of the nanocrystalline film is very flat, and no crack, large particle agglomeration and blocky crystal appear; as can be seen from the high-magnification SEM image shown in FIG. 2, Zn-doped TiO2The nanocrystalline film presents a uniform porous network structure, the size of the nanocrystals is very uniform, and the structure can provide high surface area and high porosity, and is beneficial to deposition of quantum dots and permeation and full contact of electrolyte in a battery.
As can be seen from the TEM image of the nanocrystalline porous film shown in FIG. 3, Zn-doped TiO2The nano-crystal has good dispersibility, the size distribution of the particles is uniform (10-50nm), and large-size blocky crystals are not generated; as can be seen from the SAED pattern of the nano-crystalline porous membrane shown in FIG. 4, Zn-doped TiO was2The nanocrystals exhibit polycrystalline properties.
Different concentrations of Zn-doped TiO as shown in FIG. 52The absorption spectrogram of the nanocrystalline film can show that as the Zn concentration is increased from 0% to 50%, the Zn is doped with TiO2The absorption edge of the nanocrystalline film undergoes red shift, which indicates that: TiO due to introduction of impurity energy level2The spectral band gap of the film narrows with increasing Zn concentration;
different concentrations of Zn-doped TiO as shown in FIG. 62As can be seen from the photoluminescence spectra of the nanocrystalline films, each doped sample has a weak emission peak around 389nm, which is band edge emission, also called exciton emission, and the band edge emission peak increases with the increase of the Zn concentration. In addition to this, two samples at concentrations of 30% and 50% showed another broad emission peak around 550nm, and the peak intensity of the sample at concentration of 50% was significantly higher than that of the 30% sample. The emission peak at 550nm is mainly from the deep level defect of the material, also called surface state emission, and the result shows that as the Zn concentration increases, the surface state increases, and the electron recombination also increasesIt is enhanced, which is disadvantageous to the improvement of battery performance.
Different concentrations of Zn-doped TiO as shown in FIG. 72The battery I-V curve of the nanocrystalline photoanode shows that when the Zn concentration is 10%, the efficiency of the battery is optimal, and the factors for improving the Zn concentration mainly come from the improvement of current density and open-circuit voltage; when the Zn concentration is 30% and 50%, the performance of the battery is greatly reduced, mainly from the reduction of the current density, because the high concentration Zn incorporation introduces a large amount of deep level defects, and photoelectrons are severely recombined in a surface state, resulting in the reduction of the current density.
Claims (9)
1. Zn-doped TiO2The preparation method of the nanocrystalline photoanode is characterized by comprising the following steps of,
step 1: preparation of Ti and Zn ion solution
Step 1.1: ultrasonically cleaning Ti powder with deionized water and ethanol, ultrasonically cleaning Zn powder with deionized water and ethanol, and then respectively drying the cleaned Ti powder and Zn powder in a drying oven until the deionized water and the ethanol are completely evaporated;
step 1.2: weighing Zn powder and Ti powder treated in the step 1.1 according to a molar ratio of 0-0.5:1, and mixing to obtain mixed metal powder;
step 1.3: dispersing the mixed metal powder in an HCl solution with the mass concentration of 20-30%, standing for 5-7 days at room temperature until no bubbles are generated, obtaining an acidic Ti-Zn ion solution, and finally diluting the Ti-Zn ion solution by 5-10 times by using deionized water to obtain a diluted solution;
step 2: preparation of Zn-doped TiO2Precursor body
Step 2.1: preparing 1mol/L alkaline solution, adding the alkaline solution into the diluted solution under magnetic stirring, wherein the volume ratio of the alkaline solution to the diluted solution is 2-2.5:1, and stopping adding and stirring until no blue precipitate is generated to obtain blue emulsion;
step 2.2: standing the blue emulsion for 5-7 days to generate a white precipitate;
step 2.3: mixing the white colorCentrifugally cleaning the precipitate with deionized water until the pH of the cleaned deionized water is reduced to 6.5-7.5 to obtain Zn-doped TiO2A precursor;
and step 3: preparation of Zn-doped TiO2Nanocrystal
Step 3.1: weighing Zn-doped TiO2Precursor, doping the Zn with TiO2Uniformly dispersing the precursor into absolute ethyl alcohol to obtain precursor ethyl alcohol liquid;
step 3.2: weighing ethyl cellulose and terpineol, and dissolving the ethyl cellulose and the terpineol in absolute ethyl alcohol to obtain a mixed solution A;
step 3.3: adding the mixed solution A into the precursor ethanol solution obtained in the step 3.1 under magnetic stirring, stirring for 3-4 days to obtain a mixed solution B, placing the mixed solution B into a water bath at 60-70 ℃, stirring until absolute ethanol is completely volatilized, transferring the remainder into a crucible, annealing in a muffle furnace at 400-500 ℃ for 4-6h, naturally cooling to room temperature, and finally grinding the powder obtained by annealing for 3-4h to obtain Zn-doped TiO2A nanocrystal;
and 4, step 4: preparation of Zn-doped TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn-doped TiO2Adding the nanocrystalline into absolute ethyl alcohol, performing ultrasonic treatment for 8-10 times at intervals, stirring, adding terpineol, and performing ultrasonic treatment for 2-4 times at intervals, stirring to obtain mixed slurry;
step 4.2: weighing ethyl cellulose again, dissolving the ethyl cellulose in absolute ethyl alcohol to obtain ethyl cellulose ethanol solution, adding the ethyl cellulose ethanol solution into the mixed slurry obtained in the step 4.1, performing ultrasonic treatment and stirring for 2-4 times, stirring for 6-8 days, and stirring in a water bath at the temperature of 60-80 ℃ until the absolute ethyl alcohol is completely volatilized to obtain Zn-doped TiO2A nanocrystalline slurry;
and 5: preparation of quantum dot sensitized Zn doped TiO2Nanocrystalline porous film and photoanode
Step 5.1: in the presence of TiO2Coating a layer of Zn-doped TiO on FTO conductive glass of the compact layer by adopting a screen printing technology2A nanocrystalline slurryStanding in air for 8-10min, heating in a drying oven at 60-80 deg.C for 5-10min after the slurry flow is balanced, and coating the Zn-doped TiO2The steps of nanocrystalline slurry are cycled for 4 times, and finally the coated Zn-doped TiO is added2Putting the nanocrystalline slurry film into a muffle furnace, heating from room temperature to 450 ℃ at the speed of 3 ℃/min, and annealing for 30-35min to obtain Zn-doped TiO2A nanocrystalline porous film;
step 5.2: doping Zn with TiO by SILAR method2And CdS/CdSe/ZnS quantum dots are deposited on the surface of the nanocrystalline porous membrane to obtain the photo-anode for the battery.
2. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that the deionized water and ethanol in the step 1.1 are cleaned by ultrasonic for 3-4 times.
3. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that in the step 1.3, 90ml of HCl solution is matched with every 3-4g of mixed metal powder.
4. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that the alkaline solution in the step 2.1 is one of potassium hydroxide, sodium hydroxide or ammonia water.
5. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that in the step 3.1, every 3g of milky Zn-doped TiO2The precursor is prepared by 100ml of absolute ethyl alcohol.
6. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that, in the step 3.1, Zn is doped with TiO2The precursor is dispersed into absolute ethyl alcohol by an ultrasonic stirring mode.
7. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that in the step 3.2, every 1.5g of ethyl cellulose and 12g of terpineol are matched with 100ml of absolute ethyl alcohol.
8. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that every 1g of Zn doped TiO in the step 4.12The proportion of the nano-crystal is 20ml of absolute ethyl alcohol; 4.1, the interval ultrasound and stirring are ultrasound for 1 hour and then stirring for 2 hours; step 4.1 the terpineol and the Zn-doped TiO2The mass ratio of the nano-crystals is 1: 4.
9. Zn-doped TiO according to claim 12The preparation method of the nanocrystalline photoanode is characterized in that in the step 4.2, 20ml of absolute ethyl alcohol is matched with every 0.5g of ethyl cellulose, and in the step 4.2, the ultrasonic treatment and the stirring are firstly carried out for 1 hour and then are carried out for 1 hour.
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