CN109166732A - A kind of Zn doping TiO2The preparation method of nanocrystalline light anode - Google Patents
A kind of Zn doping TiO2The preparation method of nanocrystalline light anode Download PDFInfo
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- CN109166732A CN109166732A CN201811032179.3A CN201811032179A CN109166732A CN 109166732 A CN109166732 A CN 109166732A CN 201811032179 A CN201811032179 A CN 201811032179A CN 109166732 A CN109166732 A CN 109166732A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
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- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of Zn to adulterate TiO2The preparation method of nanocrystalline light anode, specific steps are as follows: the metal Ti powder for setting molar ratio and Zn powder are dissolved in hydrochloric acid solution preparation Ti ion and Zn solion, preparation Zn doping TiO2Presoma, preparation Zn adulterate TiO2Nanocrystalline, preparation Zn adulterates TiO2Nanocrystalline slurry prepares quantum dot sensitized Zn doping TiO2Nanocrystalline light anode.Simple process of the invention, it is low in cost, can scale, reproducible, two technologies of most critical are in entire technique: metal Ti and the Zn dissolution in acid prepare presoma ion；Obtaining, there is good dispersion Zn to adulterate TiO2Nanocrystalline annealing process.It is adulterated using light anode prepared by the present invention by Zn and reduces TiO2The band gap of material improves electron transport property, to improve the photoelectric conversion performance of battery.
Description
Technical field
The invention belongs to solar battery light anode preparation method technical fields, and in particular to a kind of Zn doping TiO2Nanometer
The preparation method of brilliant light anode.
Background technique
In recent years, the demand with people to the energy is continuously increased and the lasting reduction of fossil fuel reserves, finds one kind
New abundance, environmentally protective alternative energy source have become one of important topic of current scientific research.Solar energy takes as one kind
Natural energy source not to the utmost be increasingly subject to global concern, especially solar energy is converted into the solar battery of electric energy
Research has become the hot spot studied at present.
Sensitization solar battery because its is at low cost, environmental-friendly, manufacture craft is simple, acceptable transfer efficiency due to by
Concern.In the latest 20 years, people are that enhancing battery efficiency has carried out many research work, such as semiconductor optical anode, sensitizer (dye
Material or quantum dot), electrolyte and the improvement to electrode.In sensitization solar battery structure, semiconductor optical anode is battery
One of important component, major function are absorption sensitizer and transmission light induced electron.Multimetal oxide is applied
In light anode, such as TiO2、ZnO、SnO2And ZrO2.In these metal oxides, nano-TiO2It is good with chemical stability, at
The advantages that this is low, charge transport ability is strong, is a kind of good candidate material.Optical anode material has high electron transport ability
It is one of the significant concern of battery performance.It is well known that metal ion mixing is adjustment TiO2Material property (fermi level, band
Gap and conductivity) the important method of one kind.Zn adulterates TiO2It is a kind of n-type doping material, wherein excessive negative electrical charge helps
In the transmission of electronics, and Zn doping also has adjusted TiO2The optical band gap and fermi level of material.Currently, Zn adulterates TiO2?
In sensitization solar battery for light anode research there are reports [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 Energy Materials&Solar Cells,
2016,157:447–453；J.Cao,Y.Zhu,X.Yang,et al.Solar Energy Materials&Solar Cells,
2016,157:814-819.], analysis and summary are found, adulterate TiO about Zn in document2The preparation of optical anode material, on the one hand,
The titanium tetrachloride of use, isopropyl titanate, butyl titanate are as Ti4+Source and soluble zinc salt (zinc acetate, zinc nitrate, zinc chloride,
Zinc sulfate) it is used as Zn2+Source, although Zn2+The advantage of lower cost in source, but Ti4+The cost is relatively high in source, and these Ti4+Source
It is easy to hydrolyze in air, be difficult to control；On the other hand, the sol-gel method of use is nanocrystalline in annealing process holds very much
Easily reunite.
Summary of the invention
The object of the present invention is to provide a kind of Zn to adulterate TiO2The preparation method of nanocrystalline light anode solves existing molten
Glue-gel method preparation Zn adulterates TiO2The cost is relatively high and nanocrystalline easy hair during recrystallization annealing temperature for raw material in nano material
The problem of raw reunion, bad dispersibility.
The technical scheme adopted by the invention is that a kind of Zn adulterates TiO2The preparation method of nanocrystalline light anode is specific to grasp
Steps are as follows for work:
Step 1: preparation Ti and Zn solion
Step 1.1: deionized water and EtOH Sonicate is respectively adopted in Ti powder and is cleaned, by Zn powder be respectively adopted deionized water and
EtOH Sonicate cleaning, then again respectively by after cleaning Ti powder and Zn powder that deionized water is dried in drying box is complete with ethyl alcohol
Evaporation；
Step 1.2: being that 0-0.5:1 weighs the Zn powder handled by step 1.1 and the mixing of Ti powder according to molar ratio, mixed
Close metal powder；
Step 1.3: mixed metal powder being dispersed in the HCl solution that mass concentration is 20-30%, at room temperature
5-7 days are stood, until no longer generating bubble, obtains acidity Ti-Zn solion, it is finally with deionized water that Ti-Zn ion is molten
Liquid dilutes 5-10 times, obtains dilute solution；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the alkaline solution of 1mol/L, and alkaline solution is added to dilute solution under magnetic stirring
In, alkaline solution and dilute solution volume ratio are 2-2.5:1, stop addition and stirring when no longer generating blue precipitate, obtain
To blue emulsion；
Step 2.2: blue emulsion being stood 5-7 days, generates white precipitate；
Step 2.3: white precipitate being used into deionized water eccentric cleaning, until the deionized water PH after having cleaned is down to
6.5-7.5 obtaining Zn adulterates TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing Zn doping TiO2Zn is adulterated TiO by presoma2Presoma is uniformly distributed in dehydrated alcohol,
Obtain precursor ethanol liquid；
Step 3.2: ethyl cellulose and terpinol are weighed, ethyl cellulose and terpinol are dissolved in dehydrated alcohol,
Obtain mixed solution A；
Step 3.3: under magnetic stirring will mixed solution A be added step 3.1 precursor ethanol liquid in, stirring 3-4 days it
Afterwards, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 60-70 DEG C is volatilized completely to dehydrated alcohol, then will
Residue is transferred in crucible, and cooled to room temperature after the 4-6h that anneals in 400-500 DEG C of Muffle furnace will finally anneal
The powder mull 3-4h arrived obtains Zn and adulterates TiO2It is nanocrystalline；
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing Zn doping TiO2It is nanocrystalline to be added in dehydrated alcohol, pass through 8-10 minor tick ultrasound, stirring
Terpinol is added later, is continued 2-4 minor tick ultrasound, stirring, is obtained mixed slurry；
Step 4.2: weighing ethyl cellulose again, and ethyl cellulose is dissolved in dehydrated alcohol, obtain ethyl fibre
Ethanol is tieed up, in the mixed slurry that ethyl cellulose ethanol addition step 4.1 is obtained, by 2-4 ultrasound and stirring, then
After stirring in 6-8 days, in 60-80 DEG C of stirred in water bath until dehydrated alcohol volatilizees completely, obtains Zn and adulterate TiO2It receives
Rice magma material；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2One layer of Zn doping is coated using screen printing technique on the FTO electro-conductive glass of compacted zone
TiO2Nanocrystalline slurry, then places 8-10min in air, is put into 60-80 DEG C of drying box after waiting pulp flows to balance
5-10min is heated, above-mentioned coating Zn is adulterated into TiO2The step of nanocrystalline slurry, recycles 4 times, and the Zn of coating is finally adulterated TiO2
Nanocrystalline slurry film is put into Muffle furnace, with the rate of 3 DEG C/min from room temperature to 450 DEG C of annealing 30-35min, obtains Zn
Adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
The features of the present invention also characterized in that
Step 1.1 deionized water and EtOH Sonicate clean 3-4 times.
The 90ml HCl solution of the mixed metal powder matched proportion density 20-30% of every 3-4g in step 1.3.
Alkaline solution in step 2.1 is one of potassium hydroxide, sodium hydroxide or ammonium hydroxide.
The emulsus Zn of every 3g adulterates TiO in step 3.12Presoma matches 100ml dehydrated alcohol.
Zn is adulterated TiO by step 3.12Presoma is distributed in dehydrated alcohol by way of ultrasonic agitation.
The ethyl cellulose of every 1.5g and 12g terpinol match 100ml dehydrated alcohol in step 3.2.
The Zn of every 1g adulterates TiO in step 4.12Nanocrystalline proportion 20ml dehydrated alcohol；The interval ultrasound of step 4.1 is stirred
Mix be first ultrasound 1h, be stirred for 2h；Step 4.1 terpinol and Zn adulterate TiO2Nanocrystalline mass ratio is 1:4.
The ethyl cellulose of every 0.5g matches 20ml dehydrated alcohol in step 4.2, and step 4.2 ultrasound and stirring are first to stir
1h, again ultrasound 1h.
The beneficial effects of the present invention are: a kind of Zn of the invention adulterates TiO2The preparation process of nanocrystalline light anode is simple,
It is low in cost, can scale, reproducible, the technology of most critical is before metal Ti and Zn are prepared in acid solution in entire technique
It drives body ion and obtains Zn and adulterate TiO2Nanocrystalline annealing process.Being adulterated using light anode prepared by the present invention by Zn is reduced
TiO2The band gap of material can enhance photo-generate electron-hole to the separation in material interface, be mixed by N-shaped Zn and provide excessive bear
Charge can enhance TiO2The electron transport ability of material, to improve the photoelectric conversion performance of battery.
Detailed description of the invention
Fig. 1 is a kind of Zn doping TiO of the present invention2The low power number SEM of nanocrystalline porous film schemes；
Fig. 2 is a kind of Zn doping TiO of the present invention2The high magnification numbe SEM of nanocrystalline porous film schemes；
Fig. 3 is a kind of Zn doping TiO of the present invention2The TEM of nanocrystalline porous film schemes；
Fig. 4 is a kind of Zn doping TiO of the present invention2Nanocrystalline porous film SAED selected area electron diffraction figure；
Fig. 5 is various concentration Zn doping TiO of the invention2Nanocrystalline porous film abosrption spectrogram；
Fig. 6 is various concentration Zn doping TiO of the invention2Nanocrystalline porous film photoluminescence spectra figure；
Fig. 7 is various concentration Zn doping TiO of the invention2Nanocrystalline light anode cell I-V curves.
Specific embodiment
A kind of Zn provided by the invention adulterates TiO2The preparation method of nanocrystalline light anode, operating procedure are as follows:
Step 1: preparation Ti and Zn solion
Step 1.1: metal Ti powder being cleaned 3-4 times using deionized water and EtOH Sonicate, Zn powder is used into deionized water
With EtOH Sonicate clean 3-4 time, then again respectively by after cleaning Ti powder and Zn powder be dried in drying box deionized water and
Ethyl alcohol evaporating completely；
Step 1.2: being the Zn powder and Ti that 0-0.5:1 weighs step 1.1 processing according to molar ratio, Zn powder and Ti are mixed
To mixed metal powder；
Step 1.3: the mixed metal powder being dispersed in the HCl solution that mass concentration is 20-30%, the gold of every 3-4g
Belonging to mixed powder needs 90ml HCl solution, stands 5-7 days at room temperature, until no longer generate bubble, acquisition acidity Ti-Zn from
Ti-Zn solion is finally diluted 5-10 times with deionized water, obtains dilute solution by sub- solution；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the alkaline solution of 1mol/L, and be under magnetic stirring added slowly to the alkaline solution
In the dilute solution solution, the alkaline solution and dilute solution volume ratio are 2-2.5:1, until no longer generating blue precipitate
When stop stirring, obtain blue emulsion；
Alkaline solution described in step 2.1 is one of potassium hydroxide, sodium hydroxide or ammonium hydroxide.
Step 2.2: the blue emulsion being stood 5-7 days, until emulsion no longer generates bubble and the life that bleaches completely
At white precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until PH is down to 6.5-7.5, obtains emulsus
Zn adulterate TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing Zn doping TiO2The emulsus Zn is adulterated TiO by presoma2Presoma ultrasonic agitation is uniform
It is distributed in dehydrated alcohol, the emulsus Zn of every 3g adulterates TiO2Presoma matches 100ml dehydrated alcohol, obtains precursor ethanol
Liquid；
Step 3.2: weighing ethyl cellulose and terpinol, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol
In, the ethyl cellulose and 12g terpinol of every 1.5g matches 100ml dehydrated alcohol, obtains mixed solution A；
Step 3.3: under magnetic stirring will mixed solution A be added step 3.1 precursor ethanol liquid in, stirring 3-4 days it
Afterwards, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 60-70 DEG C is volatilized completely to dehydrated alcohol, then will
Residue is transferred in crucible, and cooled to room temperature after the 4-6h that anneals in 400-500 DEG C of Muffle furnace will finally anneal
The powder mull 3-4h arrived obtains Zn and adulterates TiO2It is nanocrystalline；
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2Nanocrystalline to be added in dehydrated alcohol, every 1g Zn adulterates TiO2It is nanocrystalline
20ml dehydrated alcohol is matched, after 8-10 minor tick ultrasound, stirring, the interval ultrasound, stirring are first ultrasound 1h, again
Stir 2h；Terpinol is added, the terpinol and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4, continues 2-4 minor tick
Ultrasound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again and be dissolved in dehydrated alcohol, the ethyl cellulose of every 0.5g matches 20ml
Dehydrated alcohol, by 2-4 ultrasound and stirring, the ultrasound and stirring are first to stir 1h, again ultrasound 2h, using 6-8
After it stirring, continue stirring in 60-80 DEG C of water-bath and volatilize completely to dehydrated alcohol, obtains Zn and adulterate TiO2Nanometer magma
Material；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2The FTO electro-conductive glass of compacted zone coats one layer of Zn using screen printing technique and mixes
Miscellaneous TiO2Nanocrystalline slurry, then places 8-10min in air, and 60-80 DEG C of drying box is put into after waiting pulp flows to balance
Above-mentioned coating Zn is adulterated TiO by middle heating 5-10min2The wet film of coating is put into Muffle after nanocrystalline slurry stage circulation 4 times
In furnace, with the rate of 3 DEG C/min from room temperature to 450 DEG C of annealing 30-35min, obtains Zn and adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
Deposition about CdS/CdSe/ZnS quantum dot is universal method, (CdS quantum dot deposition: compound concentration difference
For the Cd of 0.1M2+(Cd(NO3)2Or Cd (OAc)2) and S2-(Na2Zn is adulterated TiO using SILAR method by S) solution 50ml2It is porous
Film alternately immerses the above two kinds of solution prepared, and reacts on its surface and generates CdS quantum dot.CdSe quantum dot deposition: with KBH4
For reducing agent, SeO is restored in deionized water2Or Se is made in Se powder2-(whole process is passed through the solution that concentration is 0.05mol/L
Inert gas shielding), and by Cd (NO3)2(or Cd (OAc)2) it is dissolved in the Cd that deionized water compound concentration is 0.05mol/L2+It is molten
The Zn that deposited CdS quantum dot is adulterated TiO using SILAR method (successive ionic layer adsorption and reaction) by liquid2Perforated membrane alternately soaks
Two kinds of solution for entering the above preparation react on its surface and generate CdSe quantum dot.ZnS quantum dot deposits: compound concentration is respectively
The Zn of 0.1M2+(Zn(NO3)2Or Zn (OAc)2) and S2-(Na2S) solution 50ml will deposited CdS/CdSe amount using SILAR method
The Zn of son point adulterates TiO2Perforated membrane alternately immerses the above two kinds of solution prepared, and reacts on its surface and generates ZnS passivation layer.
Preparation method of the invention applies also for other acid-soluble metal oxides and doping oxide nanometer
The preparation of grain, for example, Al, Cu adulterate TiO2Nano particle, Al, Cu doping zinc oxide nanometer particle, SnO2With doping SnO2Nanometer
Grain can be used in the preparation of nanocrystalline light anode.
Preparation method explanation: the present invention is dissolved in HCl solution using high pure metal Ti powder and Zn powder at room temperature, obtains
Ti3+With Zn2+Ion, using alkali (OH-) solution is injected into Ti3+With Zn2+It reacts, obtains Ti (OH) in solion3·Zn(OH)2
Blue precipitate, and blue precipitate is completely oxidized to Ti (OH) in air4·Zn(OH)2White precipitate, using ethyl cellulose
With terpinol as annealing adjuvant, by itself and Ti (OH)4·Zn(OH)2Uniformly mixing, after annealing, acquisition is of uniform size, divides
It dissipates the good Zn of property and adulterates TiO2It is nanocrystalline, and prepare the Zn doping TiO for being suitable for silk-screen printing2Nanocrystalline slurry, using silk screen
Printing technology and annealing process prepare porous Zn doping TiO2Nanocrystalline light anode.Zn of the invention adulterates TiO2Nanocrystalline light
Anode preparation process is simple, it is low in cost, can scale, reproducible, in entire technique the technology of most critical be metal Ti with
Zn prepares presoma ion in acid solution and obtains Zn doping TiO2Nanocrystalline annealing process.Using light prepared by the present invention
Anode is adulterated by Zn reduces TiO2The band gap of material can enhance photo-generate electron-hole to the separation in material interface, pass through n
Type Zn, which mixes, provides excessive negative electrical charge, can enhance TiO2The electron transport ability of material, to improve the photoelectric conversion of battery
Energy.
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
Step 1: preparation Ti and Zn solion
Step 1.1: metal Ti powder is cleaned 3 times using deionized water and EtOH Sonicate, by Zn powder using deionized water and
EtOH Sonicate clean 3 times, then again respectively by after cleaning Ti powder and Zn powder deionized water and ethyl alcohol are dried in drying box
Evaporating completely；
Step 1.2: being that 0:10 weighs the dry Zn powder and Ti of step 1.1 according to molar ratio, Zn powder and Ti are mixed to get
Mixed metal powder；
Step 1.3: the metal being mixed into powder and is dispersed in the HCl solution that mass concentration is 20%, the metal of every 3g mixes powder
90ml HCl solution is needed, stands 5-7 days at room temperature, until no longer generating bubble, it is molten to obtain acidity Ti-Zn ion
Ti-Zn solion is finally diluted 5 times with deionized water, obtains dilute solution by liquid；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the potassium hydroxide of 1mol/L, and be under magnetic stirring added slowly to the potassium hydroxide
In the dilute solution, the potassium hydroxide and dilute solution volume ratio are 2:1, stop stirring when no longer generating blue precipitate
It mixes, obtains blue emulsion；
Step 2.2: the blue emulsion being stood 5 days, until emulsion no longer generates bubble and the generation that bleaches completely
White precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until PH is down to 6.5, obtains the Zn of emulsus
Adulterate TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing the Zn doping TiO of emulsus2The emulsus Zn is adulterated TiO by presoma2Presoma passes through ultrasound
What is stirred evenly is distributed in dehydrated alcohol, and the emulsus Zn of every 3g adulterates TiO2Presoma matches 100ml dehydrated alcohol, before obtaining
Drive body ethanol；
Step 3.2: weighing ethyl cellulose and terpinol, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol
In, the ethyl cellulose and 12g terpinol of every 1.5g matches 100ml dehydrated alcohol, obtains mixed solution A；
Step 3.3: gradually the mixed solution A being added in the precursor ethanol liquid under magnetic stirring, stirs 3 days
Later, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 60 DEG C is volatilized completely to dehydrated alcohol, then
Residue is transferred in ceramic crucible, takes out, is done after cooled to room temperature after the 6h that anneals in 400 DEG C of Muffle furnace
The dried powder is finally ground 3h by dry powder, is obtained Zn and is adulterated TiO2It is nanocrystalline；
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2Nanocrystalline to be added in dehydrated alcohol, every 1g Zn adulterates TiO2It is nanocrystalline
Proportion 20ml dehydrated alcohol, after 8 minor ticks ultrasound, stirring, the interval ultrasound, stirring are first ultrasound 1h, stir again
Mix 2h；Terpinol is added, the terpinol and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4, and it is super to continue 2 minor ticks
Sound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again and be dissolved in dehydrated alcohol, the ethyl cellulose of every 0.5g matches 20ml
Dehydrated alcohol, by 2 ultrasounds and stirrings, the ultrasound and stirring were first to stir 1h, again ultrasound 2h, using 6 days
After stirring, continue stirring in 60 DEG C of water-bath and volatilize completely to dehydrated alcohol, obtains Zn and adulterate TiO2Nanocrystalline slurry；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2The FTO electro-conductive glass of compacted zone coats one layer of Zn using screen printing technique and mixes
Miscellaneous TiO2Nanocrystalline slurry, then places 8min in air, is put into 60 DEG C of drying box and heats after waiting pulp flows to balance
Above-mentioned coating Zn is adulterated TiO by 5min2The wet film of coating is put into Muffle furnace by nanocrystalline slurry stage after recycling 4 times, with 3
DEG C/rate of min from room temperature to 450 DEG C of annealing 30min, obtain Zn and adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
Embodiment 2
Step 1: preparation Ti and Zn solion
Step 1.1: metal Ti powder is cleaned 4 times using deionized water and EtOH Sonicate, by Zn powder using deionized water and
EtOH Sonicate clean 4 times, then again respectively by after cleaning Ti powder and Zn powder deionized water and ethyl alcohol are dried in drying box
Evaporating completely；
Step 1.2: being that 1:9 weighs the dry Zn powder and Ti of step 1.1 according to molar ratio, Zn powder and Ti are mixed to get mixed
Close metal powder；
Step 1.3: the metal being mixed into powder and is dispersed in the HCl solution that mass concentration is 30%, the metal of every 4g mixes powder
90ml HCl solution is needed, stands 7 days at room temperature, until no longer generating bubble, obtains acidity Ti-Zn solion,
Ti-Zn solion is finally diluted 10 times with deionized water, obtains dilute solution；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the sodium hydroxide of 1mol/L, and be under magnetic stirring added slowly to the sodium hydroxide
In the dilute solution, the sodium hydroxide and dilute solution volume ratio are 2.2:1, stopping when no longer generating blue precipitate
Stirring, obtains blue emulsion；
Step 2.2: the blue emulsion being stood 7 days, until emulsion no longer generates bubble and the generation that bleaches completely
White precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until PH is down to 7.5, obtains the Zn of emulsus
Adulterate TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing the Zn doping TiO of emulsus2The emulsus Zn is adulterated TiO by presoma2Presoma passes through ultrasound
What is stirred evenly is distributed in dehydrated alcohol, and the emulsus Zn of every 3g adulterates TiO2Presoma matches 100ml dehydrated alcohol, before obtaining
Drive body ethanol；
Step 3.2: weighing ethyl cellulose and terpinol, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol
In, the ethyl cellulose and 12g terpinol of every 1.5g matches 100ml dehydrated alcohol, obtains mixed solution A；
Step 3.3: gradually the mixed solution A being added in the precursor ethanol liquid under magnetic stirring, stirs 4 days
Later, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 70 DEG C is volatilized completely to dehydrated alcohol, then
Residue is transferred in ceramic crucible, takes out, is done after cooled to room temperature after the 4h that anneals in 500 DEG C of Muffle furnace
The dried powder is finally ground 4h by dry powder, is obtained Zn and is adulterated TiO2It is nanocrystalline.
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2Nanocrystalline to be added in dehydrated alcohol, every 1g Zn adulterates TiO2It is nanocrystalline
Proportion 20ml dehydrated alcohol, after 10 minor ticks ultrasound, stirring, the interval ultrasound, stirring are first ultrasound 1h, stir again
Mix 2h；Terpinol is added, the terpinol and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4, and it is super to continue 4 minor ticks
Sound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again and be dissolved in dehydrated alcohol, the ethyl cellulose of every 0.5g matches 20ml
Dehydrated alcohol, by 4 ultrasounds and stirrings, the ultrasound and stirring were first to stir 1h, again ultrasound 2h, using 8 days
After stirring, continue stirring in 80 DEG C of water-bath and volatilize completely to dehydrated alcohol, obtains Zn and adulterate TiO2Nanocrystalline slurry；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2The FTO electro-conductive glass of compacted zone coats one layer of Zn using screen printing technique and mixes
Miscellaneous TiO2Nanocrystalline slurry, then places 10min in air, is put into 80 DEG C of drying box and heats after waiting pulp flows to balance
Above-mentioned coating Zn is adulterated TiO by 10min2The wet film of coating is put into Muffle furnace by nanocrystalline slurry stage after recycling 4 times, with 3
DEG C/rate of min from room temperature to 450 DEG C of annealing 35min, obtain Zn and adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
Embodiment 3
Step 1: preparation Ti and Zn solion
Step 1.1: metal Ti powder is cleaned 3 times using deionized water and EtOH Sonicate, by Zn powder using deionized water and
EtOH Sonicate clean 4 times, then again respectively by after cleaning Ti powder and Zn powder deionized water and ethyl alcohol are dried in drying box
Evaporating completely；
Step 1.2: being that 3:7 weighs the dry Zn powder and Ti of step 1.1 according to molar ratio, Zn powder and Ti are mixed to get mixed
Close metal powder；
Step 1.3: the metal being mixed into powder and is dispersed in the HCl solution that mass concentration is 25%, the metal of every 3.5g is mixed
Powder needs 90ml HCl solution, stands 6 days at room temperature, until no longer generating bubble, it is molten to obtain acidity Ti-Zn ion
Ti-Zn solion is finally diluted 8 times with deionized water, obtains dilute solution by liquid；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the ammonium hydroxide of 1mol/L, and be under magnetic stirring added slowly to the sodium hydroxide described
In dilute solution, the sodium hydroxide and dilute solution volume ratio are 2.5:1, stop stirring when no longer generating blue precipitate
It mixes, obtains blue emulsion；
Step 2.2: the blue emulsion being stood 6 days, until emulsion no longer generates bubble and the generation that bleaches completely
White precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until PH is down to 7, the Zn for obtaining emulsus mixes
Miscellaneous TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing Zn doping TiO2The Zn is adulterated TiO by presoma2The uniform dispersion of presoma ultrasonic agitation
Into dehydrated alcohol, the emulsus Zn of every 3g adulterates TiO2Presoma matches 100ml dehydrated alcohol, obtains precursor ethanol liquid；
Step 3.2: weighing ethyl cellulose and terpinol, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol
In, the ethyl cellulose and 12g terpinol of every 1.5g matches 100ml dehydrated alcohol, obtains mixed solution A；
Step 3.3: gradually the mixed solution A being added in the precursor ethanol liquid under magnetic stirring, stirs 3 days
Later, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 65 DEG C is volatilized completely to dehydrated alcohol, then
Residue is transferred in ceramic crucible, takes out, is done after cooled to room temperature after the 5h that anneals in 450 DEG C of Muffle furnace
The dried powder is finally ground 3.5h by dry powder, is obtained Zn and is adulterated TiO2It is nanocrystalline.
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2Nanocrystalline to be added in dehydrated alcohol, every 1g Zn adulterates TiO2It is nanocrystalline
Proportion 20ml dehydrated alcohol, after 9 minor ticks ultrasound, stirring, the interval ultrasound, stirring are first ultrasound 1h, stir again
Mix 2h；Terpinol is added, the terpinol and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4, and it is super to continue 3 minor ticks
Sound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again and be dissolved in dehydrated alcohol, the ethyl cellulose of every 0.5g matches 20ml
Dehydrated alcohol, by 3 ultrasounds and stirrings, the ultrasound and stirring were first to stir 1h, again ultrasound 2h, using 7 days
After stirring, continue stirring in 70 DEG C of water-bath and volatilize completely to dehydrated alcohol, obtains Zn and adulterate TiO2Nanocrystalline slurry；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2The FTO electro-conductive glass of compacted zone coats one layer of Zn using screen printing technique and mixes
Miscellaneous TiO2Nanocrystalline slurry, then places 9min in air, is put into 70 DEG C of drying box and heats after waiting pulp flows to balance
Above-mentioned coating Zn is adulterated TiO by 8min2The wet film of coating is put into Muffle furnace by nanocrystalline slurry stage after recycling 4 times, with 3
DEG C/rate of min from room temperature to 450 DEG C of annealing 32min, obtain Zn and adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
Embodiment 4
Step 1: preparation Ti and Zn solion
Step 1.1: metal Ti powder is cleaned 4 times using deionized water and EtOH Sonicate, by Zn powder using deionized water and
EtOH Sonicate clean 3 times, then again respectively by after cleaning Ti powder and Zn powder deionized water and ethyl alcohol are dried in drying box
Evaporating completely；
Step 1.2: being that 1:1 weighs step 1.1 treated Zn powder and Ti according to molar ratio, Zn powder and Ti are mixed to get
Mixed metal powder；
Step 1.3: the metal being mixed into powder and is dispersed in the HCl solution that mass concentration is 20%, the metal of every 4g mixes powder
90ml HCl solution is needed, stands 5 days at room temperature, until no longer generating bubble, obtains acidity Ti-Zn solion,
Ti-Zn solion is finally diluted 6 times with deionized water, obtains dilute solution；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: preparing the potassium hydroxide of 1mol/L, and be under magnetic stirring added slowly to the potassium hydroxide
In the dilute solution, the potassium hydroxide and dilute solution volume ratio are 2:1, stop stirring when no longer generating blue precipitate
It mixes, obtains blue emulsion；
Step 2.2: the blue emulsion being stood 7 days, until emulsion no longer generates bubble and the generation that bleaches completely
White precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until PH is down to 7, the Zn for obtaining emulsus mixes
Miscellaneous TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing Zn doping TiO2The Zn is adulterated TiO by presoma2Presoma passes through the dispersion stirred evenly
Into dehydrated alcohol, the emulsus Zn of every 3g adulterates TiO2Presoma matches 100ml dehydrated alcohol, obtains precursor ethanol liquid；
Step 3.2: weighing ethyl cellulose and terpinol, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol
In, the ethyl cellulose and 12g terpinol of every 1.5g matches 100ml dehydrated alcohol, obtains mixed solution A；
Step 3.3: gradually the mixed solution A being added in the precursor ethanol liquid under magnetic stirring, stirs 3 days
Later, mixed solution B is obtained, the mixed solution B is volatilized in 70 DEG C of stirred in water bath to dehydrated alcohol completely, then will
Residue is transferred in ceramic crucible, is taken out after cooled to room temperature after the 5h that anneals in 500 DEG C of Muffle furnace, is obtained drying
The dried powder is finally ground 3h by powder, is obtained Zn and is adulterated TiO2It is nanocrystalline.
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2Nanocrystalline to be added in dehydrated alcohol, every 1g Zn adulterates TiO2It is nanocrystalline
Proportion 20ml dehydrated alcohol, after 10 minor ticks ultrasound, stirring, the interval ultrasound, stirring are first ultrasound 1h, stir again
Mix 2h；Terpinol is added, the terpinol and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4, and it is super to continue 3 minor ticks
Sound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again and be dissolved in dehydrated alcohol, the ethyl cellulose of every 0.5g matches 20ml
Dehydrated alcohol, by 4 ultrasounds and stirrings, the ultrasound and stirring were first to stir 1h, again ultrasound 2h, using 7 days
After stirring, continue stirring in 70 DEG C of water-bath and volatilize completely to dehydrated alcohol, obtains Zn and adulterate TiO2Nanocrystalline slurry；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2The FTO electro-conductive glass of compacted zone coats one layer of Zn using screen printing technique and mixes
Miscellaneous TiO2Nanocrystalline slurry, then places 8min in air, is put into 60 DEG C of drying box and heats after waiting pulp flows to balance
Above-mentioned coating Zn is adulterated TiO by 10min2The wet film of coating is put into Muffle furnace by nanocrystalline slurry stage after recycling 4 times, with 3
DEG C/rate of min from room temperature to 450 DEG C of annealing 35min, obtain Zn and adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum
Point obtains the light anode for being used for battery.
For low power number SEM figure as shown in Figure 1 as can be seen that in wide area, Zn adulterates TiO2The surface of nanometer crystal film
It is very smooth, reunite without crack, without bulky grain and block-like crystal occurs；High magnification numbe SEM figure as shown in Figure 2 can be seen
Out, Zn adulterates TiO2Uniform porous network structure is presented in nanometer crystal film, and nanocrystalline size is highly uniform, and this structure can mention
For high surface area and high porosity, is conducive to the deposition of quantum dot in the battery and electrolyte permeability and comes into full contact with.
Nanocrystalline porous film TEM figure as shown in Figure 3 is as can be seen that Zn adulterates TiO2It is nanocrystalline that there is good dispersion,
And the even size distribution (10-50nm) of particle, without large-sized bulk crystals；Nanocrystalline porous film as shown in Figure 4
SAED figure is as can be seen that Zn adulterates TiO2Nanocrystalline presentation polycrystalline property.
Various concentration Zn as shown in Figure 5 adulterates TiO2Nanometer crystal film abosrption spectrogram can be seen that with Zn concentration from
0% increases to 50%, Zn doping TiO2Red shift, ABSORPTION EDGE red shift explanation: due to impurity energy level occur for the ABSORPTION EDGE of nanometer crystal film
Introducing, TiO2The spectrum band gap of film narrows with the increase of Zn concentration；
Various concentration Zn as shown in FIG. 6 adulterates TiO2Nanometer crystal film photoluminescence spectra figure can be seen that every kind of doping
Sample all has a weaker emission peak in 389nm or so, this is band-edge emission, also referred to as exciton emission, and with Zn
The increase of concentration, the enhancing of band-edge emission peak.In addition to this, two samples that concentration is 30% and 50% occur near 550nm
The emission peak of another wide scope, and concentration is apparently higher than 30% sample for the peak intensity of 50% sample.The transmitting of the position 550nm
Peak is mainly from the deep energy level defect of material, also referred to as surface state emission, and the result shows with the increase surface of Zn concentration
State increases, and electronics is compound also just to be enhanced, this is unfavorable for the raising of battery performance.
Various concentration Zn as shown in Figure 7 adulterates TiO2The cell I-V curves of nanocrystalline light anode can be seen that and work as Zn
Concentration is 10%, the efficiency optimization of battery, the raising of the factor of raising mainly from current density and open-circuit voltage；When Zn concentration
When being 30% and 50%, the performance of battery is significantly reduced, mainly from the reduction of current density, the reason is that high concentration Zn mixes
Enter to have introduced a large amount of deep energy level defect, photoelectron is serious compound in surface state generation, leads to the reduction of current density.
Claims (9)
1. a kind of Zn adulterates TiO2The preparation method of nanocrystalline light anode, which is characterized in that it is specifically implemented according to the following steps,
Step 1: preparation Ti and Zn solion
Step 1.1: Ti powder being cleaned with deionized water and EtOH Sonicate, Zn powder is cleaned with deionized water and EtOH Sonicate, so
Afterwards again by after cleaning Ti powder and Zn powder deionized water and ethyl alcohol evaporating completely are dried in drying box respectively；
Step 1.2: being that 0-0.5:1 weighs the Zn powder handled by step 1.1 and the mixing of Ti powder according to molar ratio, obtain mixing gold
Belong to powder；
Step 1.3: the mixed metal powder being dispersed in the HCl solution that mass concentration is 20-30%, at room temperature
Stand 5-7 days, until no longer generate bubble, acquisition acidity Ti-Zn solion, finally with deionized water by the Ti-Zn from
Sub- solution dilutes 5-10 times, obtains dilute solution；
Step 2: preparation Zn adulterates TiO2Presoma
Step 2.1: prepare the alkaline solution of 1mol/L, and under magnetic stirring by the alkaline solution be added to it is described dilution it is molten
In liquid, the alkaline solution and dilute solution volume ratio are 2-2.5:1, stop being added when no longer generating blue precipitate and stir
It mixes, obtains blue emulsion；
Step 2.2: the blue emulsion being stood 5-7 days, generates white precipitate；
Step 2.3: the white precipitate being used into deionized water eccentric cleaning, until the deionized water PH after having cleaned is down to
6.5-7.5 obtaining Zn adulterates TiO2Presoma；
Step 3: preparation Zn adulterates TiO2It is nanocrystalline
Step 3.1: weighing Zn doping TiO2The Zn is adulterated TiO by presoma2Presoma is uniformly distributed in dehydrated alcohol,
Obtain precursor ethanol liquid；
Step 3.2: ethyl cellulose and terpinol are weighed, the ethyl cellulose and terpinol are dissolved in dehydrated alcohol,
Obtain mixed solution A；
Step 3.3: the mixed solution A being added in precursor ethanol liquid described in step 3.1 under magnetic stirring, stirs 3-4
After it, mixed solution B is obtained, the mixed solution B stirred in water bath for being placed in 60-70 DEG C is waved completely to dehydrated alcohol
Residue, is then transferred in crucible by hair, cooled to room temperature after the 4-6h that anneals in 400-500 DEG C of Muffle furnace, most
The powder mull 3-4h that annealing is obtained afterwards obtains Zn and adulterates TiO2It is nanocrystalline；
Step 4: preparation Zn adulterates TiO2Nanocrystalline slurry
Step 4.1: weighing the Zn doping TiO2It is nanocrystalline to be added in dehydrated alcohol, by 8-10 minor tick ultrasound, stir it
After add terpinol, continue 2-4 minor tick ultrasound, stirring, obtain mixed slurry；
Step 4.2: weighing ethyl cellulose again, and the ethyl cellulose is dissolved in dehydrated alcohol, obtain ethyl fibre
Ethanol is tieed up, in the mixed slurry that ethyl cellulose ethanol addition step 4.1 is obtained, by 2-4 ultrasound and is stirred
It mixes, after stirring in 6-8 days, in 60-80 DEG C of stirred in water bath until dehydrated alcohol volatilizees completely, obtains Zn doping
TiO2Nanocrystalline slurry；
Step 5: preparing quantum dot sensitized Zn doping TiO2Nanocrystalline porous film and light anode
Step 5.1: having TiO2One layer of Zn doping is coated using screen printing technique on the FTO electro-conductive glass of compacted zone
TiO2Nanocrystalline slurry, then places 8-10min in air, is put into 60-80 DEG C of drying box after waiting pulp flows to balance
5-10min is heated, above-mentioned coating Zn is adulterated into TiO2The step of nanocrystalline slurry, recycles 4 times, and the Zn of coating is finally adulterated TiO2
Nanocrystalline slurry film is put into Muffle furnace, with the rate of 3 DEG C/min from room temperature to 450 DEG C of annealing 30-35min, obtains Zn
Adulterate TiO2Nanocrystalline porous film；
Step 5.2: TiO is adulterated in Zn using SILAR method2Nanocrystalline porous film surface deposits CdS/CdSe/ZnS quantum dot, obtains
Light anode for battery.
2. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 1.1
The deionized water and EtOH Sonicate clean 3-4 times.
3. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 1.3
Described in every 3-4g metal mix powder match 90ml HCl solution.
4. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 2.1
Described in alkaline solution be one of potassium hydroxide, sodium hydroxide or ammonium hydroxide.
5. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 3.1
Described in every 3g emulsus Zn adulterate TiO2Presoma matches 100ml dehydrated alcohol.
6. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 3.1
It is described that Zn is adulterated into TiO2Presoma is distributed in dehydrated alcohol by way of ultrasonic agitation.
7. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 3.2
Described in every 1.5g ethyl cellulose and 12g terpinol match 100ml dehydrated alcohol.
8. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 4.1
Described in every 1g Zn adulterate TiO2Nanocrystalline proportion 20ml dehydrated alcohol；Interval ultrasound, stirring are first super described in step 4.1
Sound 1h, it is stirred for 2h；Terpinol described in step 4.1 and the Zn adulterate TiO2Nanocrystalline mass ratio is 1:4.
9. Zn according to claim 1 adulterates TiO2Nanocrystalline light anode preparation method, which is characterized in that step 4.2
Described in the ethyl cellulose of every 0.5g match 20ml dehydrated alcohol, ultrasound and stirring described in step 4.2 be first stirring 1h, surpass again
Sound 1h.
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