CN107633951A - A kind of method and its application that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis - Google Patents
A kind of method and its application that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis Download PDFInfo
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Abstract
A kind of method and its application that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis, it is related to a kind of preparation method and applications of light anode.Electric transmission efficiency is low the invention aims to solving when existing mesoporous material uses as the light anode of sensitization solar battery, and the problem of compound easily occurs in transmitting procedure for photoelectron.Method：First, prepare and go deimpurity conductive substrates；2nd, TiCl is utilized4Hydrolysis prepares barrier layer；3rd, TiO is prepared with hydrothermal system2Skeleton, obtain homogeneity barrier layer/skeleton structure.The electricity conversion PCE for the inorganic quantum dot sensitized solar cell that homogeneity barrier layer/skeleton structure prepared by the present invention is prepared as the light anode of inorganic quantum dot sensitized solar cell reaches 5.45%~6.24%.The present invention can obtain homogeneity barrier layer/skeleton structure.
Description
Technical field
The present invention relates to a kind of preparation method and applications of light anode.
Background technology
In recent years, as people are continuously increased to the demand of the energy and the lasting reduction of fossil fuel reserves, find a kind of
New abundance, the green energy are as one of important topic of current scientific research.Solar energy as one kind take no
Most natural energy source is increasingly subject to global concern, and wherein solar cell can conversion solar can be directly electric energy, into
For the focus studied at present.
Quantum dot sensitized solar cell (QDSSC) is the novel solar battery based on the development of dye sensitization system, its
With advantages below：First, energy gap is adjustable, and photostability is high；2nd, there is exciton multiplier effect；3rd, there is larger delustring
Coefficient and intrinsic dipole moment, promote electron hole separation；4th, the level-density parameter of electron donor and acceptor material is easily realized；This
A little advantages allow the theoretical efficiency of quantum dot sensitized solar cell to reach 44%, have good development prospect.
Quantum dot solar cell system is made up of sandwich construction：Conductive substrates/electron transfer layer (light anode)/quantum dot
Sensitizer/electrolyte/hole transmission layer (photocathode)/metal is to electrode.But in actual charge transfer process, traditional Jie
Porous materials are as light anode primary structure, there is provided abundant nano pore adsorbs sensitizer and electron transmission；But simultaneously
Many surface contacts are exposed, a large amount of electrolyte be present in the interface of mesoporous material/conductive substrates and ohm of conductive substrates connects
Touch, electronics can occur serious compound at this interface, and therefore, what is prepared using traditional mesoporous material as light anode is inorganic
Quantum dot sensitized solar battery efficiency value it is low, about 0.27%~2.15%.
The content of the invention
The invention aims to solve electronics when existing mesoporous material uses as the light anode of sensitization solar battery
Efficiency of transmission is low, and the problem of compound easily occurs in transmitting procedure for photoelectron, and provides one kind and prepared using titanium tetrachloride hydrolysis
The method and its application of homogeneity barrier layer/skeleton structure.
A kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis, it is specifically complete according to the following steps
Into：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 2 times~4 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtain clean conductive substrates；
2nd, TiCl is utilized4Hydrolysis prepares barrier layer：
1., under ice-water bath compound concentration be 20mmol/L~60mmol/L titanium tetrachloride aqueous solution, in ice after sealing
Under water-bath and mixing speed is that 1h~3h is stirred under 50r/min~80r/min, obtains barrier layer solution；
2., the conducting surface of clean conductive substrates be downwardly inclined be fixed in beaker, then by beaker in temperature be 50 DEG C
Constant temperature 0.5h~2h at~80 DEG C；
3., to step 2,2. middle temperature is that barrier layer solution is poured into 50 DEG C~80 DEG C of beaker, then in temperature be 50 DEG C
Constant temperature stands 1h~3h at~80 DEG C, and conductive substrates are taken out after reaction, and conductive substrates are cleaned 3 times~5 times using distilled water, then
Conductive substrates are cleaned 3 times~5 times using absolute ethyl alcohol, finally dried up using nitrogen；Conductive substrates are put into temperature as 400 DEG C
In~650 DEG C of tube furnace, then calcining at constant temperature 0.5h~2h in temperature is 400 DEG C~650 DEG C of tube furnace, in conductive substrates
Deposition has N-type semiconductor TiO2Film, barrier layer is served as, obtain barrier layer/conductive substrates；
Step 2 3. described in the volume of barrier layer solution and the volumetric ratio of beaker be (0.6~0.75):1；
3rd, TiO is prepared with hydrothermal system2Skeleton：
1., into distilled water add mass fraction be 32%~35% hydrochloric acid, stir, obtain hydrochloric acid solution；
Step 3 1. described in mass fraction be 32%~35% hydrochloric acid and distilled water volume ratio for (0.8~
2.3):1；
2., by step 3 1. in obtained hydrochloric acid solution be heated to 40 DEG C~70 DEG C, then temperature be 40 DEG C~70 DEG C and
Mixing speed is that butyl titanate is added dropwise under 50r/min~80r/min, obtains reaction solution I；The temperature control of reaction solution I is existed
40 DEG C~70 DEG C, then 1h~3h is stirred in the case where temperature is 40 DEG C~70 DEG C and mixing speed is 50r/min~80r/min, then from
Room temperature so is cooled to, obtains skeleton reaction solution；
Step 3 2. described in reaction solution I in the concentration of butyl titanate be 45mmol/L~60mmol/L；
3., the stop aspects of barrier layer/conductive substrates tilted be fixed in ptfe autoclave, to polytetrafluoroethyl-ne
Skeleton reaction solution is added in alkene reaction kettle, then ptfe autoclave is sealed；The ptfe autoclave of sealing is existed
Temperature is heated at constant temperature 5h~10h at 150 DEG C~200 DEG C, then cools to room temperature with the furnace；After barrier layer/conductive substrates are taken out
Calcining at constant temperature 3h~5h in the tube furnace that temperature is 400 DEG C~650 DEG C is put into, obtains homogeneity barrier layer/skeleton structure；
Step 3 3. described in skeleton reaction solution volume and ptfe autoclave volumetric ratio for (0.6~
0.75):1。
Light anode application of the homogeneity barrier layer/skeleton structure as sensitization solar battery.
The principle and advantage of the present invention：
First, the present invention is prepared for homogeneity barrier layer/skeleton structure, as electronic transmission structures, has the advantage that：Homogeneity
Contain TiO in barrier layer/skeleton structure2One-dimensional nano line array, TiO2One-dimensional nano line array structure is as electric transmission bone
Frame, one-dimensional nano structure material is applied in light anode, the transmission road of straight line is provided while increasing light path for photogenerated charge
Footpath, substantially reduce electric transmission distance；Efficiency of transmission of the electric charge in light anode is improved, and effectively inhibits photoelectron to exist
It is compound in transmitting procedure；
2nd, the present invention prepares barrier layer structure using titanium tetrachloride hydrolysis in the interface of conductive substrates/skeleton, due to logical
The mode for crossing chemical bath deposition hydrolyzes TiCl4Barrier layer is prepared, therefore the order for preparing barrier layer and skeleton is most important, this hair
It is bright compare it is common first prepare skeleton after prepare barrier layer (S-BL) and prepare skeleton (BL-S) no after first preparing barrier layer
With the light anode of preparation order, it is found that BL-S light anode structure photovoltaic performances are significantly excellent in common S-BL structures, CBL-S%
=807%~825%, CS-BL%=340%~352%, compared to S-BL structures, the interface of BL-S structures is clearly orderly, resistance
Barrier thickness is homogeneous, and thicknesses of layers is low；
3rd, the present invention prepares barrier layer using the method for titanium tetrachloride hydrolysis, and obtained stop thickness bottom is low, can be controlled in
Between 300nm~500nm, barrier layer/skeleton structure that profit is prepared in this way avoids to go out during chemical bath deposition
Existing skeleton is coupled, and the appearance of barrier layer planarization difference, the design on barrier layer blocks electrolyte and quantum in skeleton gap
Point and the direct Ohmic contacts of conductive substrates, avoid electronics and hole in electrolyte compound in conductive substrates, increase and then
Improve cell photovoltaic efficiency；
4th, it can determine that barrier layer and skeleton have same in the homogeneity barrier layer/skeleton structure of the invention prepared by XRD
The lattice parameter of sample, barrier layer/skeleton structure of homogeneity help to reduce battery equivalent internal resistance, improve electronics utilization rate；This hair
The barrier layer of bright preparation and skeleton structure both red schorl phase titanium dioxide；Introduce after homogeneity barrier layer/skeleton to inorganic
The photoelectric properties of quantum dot sensitized solar cell be obviously improved, the present invention first prepares barrier layer, after prepare skeleton, that is, make
The inorganic quantum that standby homogeneity barrier layer/skeleton structure is prepared as the light anode of inorganic quantum dot sensitized solar cell
The short circuit current J of point sensitization solar batteryscFor 12.60mA/cm2~13.32mA/cm2, open-circuit voltage VocFor 0.83V~
0.86V, fill factor, curve factor FF are 0.514~0.52, and electricity conversion PCE reaches 5.45%~6.24%；
5th, the thickness on barrier layer is 320nm~352nm in homogeneity barrier layer/skeleton structure prepared by the present invention；Skeleton
TiO2Nano wire is about 2.5 μm~2.8 μm or so, diameter about 45nm~65nm.
The present invention can obtain homogeneity barrier layer/skeleton structure light anode.
Brief description of the drawings
Fig. 1 is the SEM figures on barrier layer in barrier layer/conductive substrates prepared by the step 2 of embodiment one；
Fig. 2 is that the section SEM of barrier layer and substrate schemes in barrier layer/substrate prepared by the step 2 of embodiment one；
Fig. 3 is UV-permeable spectrogram, in Fig. 31 be glass base the UV-permeable curve of spectrum, 2 be the ultraviolet of FTO
The curve of spectrum is crossed, 3 be the UV-permeable curve of spectrum of the barrier layer/conductive substrates prepared in the step 2 of embodiment one, and 4 be implementation
The UV-permeable curve of spectrum of the barrier layer/conductive substrates prepared in the step 2 of example two；
Fig. 4 is the SEM figures of 3. homogeneity barrier layer/skeleton structure that the step 3 of embodiment one is prepared；
Fig. 5 is the section SEM figures of 3. homogeneity barrier layer/skeleton structure that the step 3 of embodiment one is prepared；
Fig. 6 is the SEM figures of S-BL light anode structures prepared by contrast test three；
Fig. 7 is the section SEM figures of S-BL light anode structures prepared by contrast test three；
Fig. 8 is X ray diffracting spectrum, and 1 is FTO main components SnO in Fig. 82Standard X-ray diffraction collection of illustrative plates, 2 be golden red
The standard X-ray diffraction collection of illustrative plates of stone, 3 be the X ray diffracting spectrum of pure barrier layer structure prepared by contrast test two, and 4 be contrast
S-BL light anode structure X ray diffracting spectrums prepared by experiment three, the 5 homogeneity barrier layers 3. prepared for the step 3 of embodiment one/
The X ray diffracting spectrum of skeleton structure, " △ " are SnO2, " " is rutile；
Fig. 9 is the current density voltage curve of inorganic quantum dot sensitized solar cell, and 1 is assembled inorganic in Fig. 9
The Current density-voltage of the inorganic quantum dot sensitized solar cell of quantum dot sensitized solar cell experiment (one) assembling is bent
Line, the 2 inorganic quantum dot sensitized solar cells assembled for the quantum dot sensitized solar cell experiment (two) of assembled inorganic
Current density voltage curve, 3 for assembled inorganic quantum dot sensitized solar cell test (three) assembling inorganic quantum
The current density voltage curve of point sensitization solar battery, 4 test (four) for the quantum dot sensitized solar cell of assembled inorganic
The current density voltage curve of the inorganic quantum dot sensitized solar cell of assembling.
Embodiment
Embodiment one：Present embodiment is that one kind prepares homogeneity barrier layer/skeleton knot using titanium tetrachloride hydrolysis
The method of structure, is specifically realized by the following steps：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 2 times~4 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtain clean conductive substrates；
2nd, TiCl is utilized4Hydrolysis prepares barrier layer：
1., under ice-water bath compound concentration be 20mmol/L~60mmol/L titanium tetrachloride aqueous solution, in ice after sealing
Under water-bath and mixing speed is that 1h~3h is stirred under 50r/min~80r/min, obtains barrier layer solution；
2., the conducting surface of clean conductive substrates be downwardly inclined be fixed in beaker, then by beaker in temperature be 50 DEG C
Constant temperature 0.5h~2h at~80 DEG C；
3., to step 2,2. middle temperature is that barrier layer solution is poured into 50 DEG C~80 DEG C of beaker, then in temperature be 50 DEG C
Constant temperature stands 1h~3h at~80 DEG C, and conductive substrates are taken out after reaction, and conductive substrates are cleaned 3 times~5 times using distilled water, then
Conductive substrates are cleaned 3 times~5 times using absolute ethyl alcohol, finally dried up using nitrogen；Conductive substrates are put into temperature as 400 DEG C
In~650 DEG C of tube furnace, then calcining at constant temperature 0.5h~2h in temperature is 400 DEG C~650 DEG C of tube furnace, in conductive substrates
Deposition has N-type semiconductor TiO2Film, barrier layer is served as, obtain barrier layer/conductive substrates；
Step 2 3. described in the volume of barrier layer solution and the volumetric ratio of beaker be (0.6~0.75):1；
3rd, TiO is prepared with hydrothermal system2Skeleton：
1., into distilled water add mass fraction be 32%~35% hydrochloric acid, stir, obtain hydrochloric acid solution；
Step 3 1. described in mass fraction be 32%~35% hydrochloric acid and distilled water volume ratio for (0.8~
2.3):1；
2., by step 3 1. in obtained hydrochloric acid solution be heated to 40 DEG C~70 DEG C, then temperature be 40 DEG C~70 DEG C and
Mixing speed is that butyl titanate is added dropwise under 50r/min~80r/min, obtains reaction solution I；The temperature control of reaction solution I is existed
40 DEG C~70 DEG C, then 1h~3h is stirred in the case where temperature is 40 DEG C~70 DEG C and mixing speed is 50r/min~80r/min, then from
Room temperature so is cooled to, obtains skeleton reaction solution；
Step 3 2. described in reaction solution I in the concentration of butyl titanate be 45mmol/L~60mmol/L；
3., the stop aspects of barrier layer/conductive substrates tilted be fixed in ptfe autoclave, to polytetrafluoroethyl-ne
Skeleton reaction solution is added in alkene reaction kettle, then ptfe autoclave is sealed；The ptfe autoclave of sealing is existed
Temperature is heated at constant temperature 5h~10h at 150 DEG C~200 DEG C, then cools to room temperature with the furnace；After barrier layer/conductive substrates are taken out
Calcining at constant temperature 3h~5h in the tube furnace that temperature is 400 DEG C~650 DEG C is put into, obtains homogeneity barrier layer/skeleton structure；
Step 3 3. described in skeleton reaction solution volume and ptfe autoclave volumetric ratio for (0.6~
0.75):1。
The principle and advantage of present embodiment：
First, present embodiment is prepared for homogeneity barrier layer/skeleton structure, as electronic transmission structures, has the advantage that：
Contain TiO in homogeneity barrier layer/skeleton structure2One-dimensional nano line array, TiO2One-dimensional nano line array structure is as electric transmission
Skeleton, one-dimensional nano structure material is applied in light anode, the transmission of straight line is provided while increasing light path for photogenerated charge
Path, substantially reduce electric transmission distance；Efficiency of transmission of the electric charge in light anode is improved, and effectively inhibits photoelectron
It is compound in transmitting procedure；
2nd, present embodiment prepares barrier layer structure using titanium tetrachloride hydrolysis in the interface of conductive substrates/skeleton, by
In hydrolyzing TiCl by way of chemical bath deposition4Barrier layer is prepared, therefore the order for preparing barrier layer and skeleton is most important,
Present embodiment, which compares, common to be prepared barrier layer (S-BL) after first preparing skeleton and prepares skeleton after first preparing barrier layer
(BL-S) light anode of different preparation orders, it is found that BL-S light anode structure photovoltaic performances are significantly excellent and tied in common S-BL
Structure, CBL-S%=807%~825%, CS-BL%=340%~352%, compared to S-BL structures, the interface of BL-S structures is clear
In order, barrier layer thickness is homogeneous, and thicknesses of layers is low；
3rd, present embodiment prepares barrier layer using the method for titanium tetrachloride hydrolysis, and obtained stop thickness bottom is low, controllable
Between 300nm~500nm, barrier layer/skeleton structure that profit is prepared in this way avoids in chemical bath deposition process system
The skeleton of middle appearance is coupled, the appearance of barrier layer planarization difference, the design on barrier layer block electrolyte in skeleton gap with
The direct Ohmic contact of quantum dot and conductive substrates, avoid electronics compound in conductive substrates with hole in electrolyte, increase
And then improve cell photovoltaic efficiency；
4th, it can determine that barrier layer and skeleton have in homogeneity barrier layer/skeleton structure of present embodiment preparation by XRD
There is same lattice parameter, barrier layer/skeleton structure of homogeneity helps to reduce battery equivalent internal resistance, improves electronics utilization rate；
Barrier layer and skeleton structure both red schorl phase titanium dioxide prepared by present embodiment；Introduce homogeneity barrier layer/skeleton
The photoelectric properties of inorganic quantum dot sensitized solar cell are obviously improved afterwards, present embodiment first prepares barrier layer, after
Skeleton is prepared, that is, light anode system of the homogeneity barrier layer/skeleton structure prepared as inorganic quantum dot sensitized solar cell
The short circuit current J of standby inorganic quantum dot sensitized solar cellscFor 12.60mA/cm2~13.32mA/cm2, open-circuit voltage
VocFor 0.83V~0.86V, fill factor, curve factor FF is 0.514~0.52, and electricity conversion PCE reaches 5.45%~6.24%；
5th, the thickness on barrier layer is 320nm~352nm in homogeneity barrier layer/skeleton structure prepared by present embodiment；Bone
Frame TiO2Nano wire is about 2.5 μm~2.8 μm or so, diameter about 45nm~65nm.
Present embodiment can obtain homogeneity barrier layer/skeleton structure light anode.
Embodiment two：Present embodiment is with the difference of embodiment one：Conduction described in step 1
Substrate is FTO electro-conductive glass, ITO electro-conductive glass or Flexible graphene substrate.Other steps are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Led in step 1
The frequency that electric substrate is cleaned by ultrasonic in toluene is 30kHz~90kHz, and the time of ultrasonic cleaning is 15min~60min, conductive
The frequency that substrate is cleaned by ultrasonic in acetone is 30kHz~90kHz, and time of ultrasonic cleaning is 15min~60min, conductive base
The frequency that bottom is cleaned by ultrasonic in absolute ethyl alcohol is 30kHz~90kHz, and the time of ultrasonic cleaning is 15min~60min, conductive
The frequency that substrate is cleaned by ultrasonic in deionized water is 30kHz~90kHz, and the time of ultrasonic cleaning is 15min~60min.Its
Its step is identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Step 2 1. in
Compound concentration is 20mmol/L~30mmol/L titanium tetrachloride aqueous solution under ice-water bath, under ice-water bath and is stirred after sealing
Speed is that 1h~2h is stirred under 50r/min~80r/min, obtains barrier layer solution.Other steps and embodiment one to
Three is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Step 2 1. in
Compound concentration is 40mmol/L~60mmol/L titanium tetrachloride aqueous solution under ice-water bath, under ice-water bath and is stirred after sealing
Speed is that 1h~1.5h is stirred under 50r/min~80r/min, obtains barrier layer solution.Other steps and embodiment one
It is identical to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Step 2 3. in
To step 2,2. middle temperature is that barrier layer solution is poured into 50 DEG C~65 DEG C of beaker, then the constant temperature in the case where temperature is 50 DEG C~65 DEG C
1h~2h is stood, conductive substrates are taken out after reaction, conductive substrates are cleaned 3 times~4 times using distilled water, reuse absolute ethyl alcohol
Conductive substrates are cleaned 3 times~4 times, finally dried up using nitrogen；Conductive substrates are put into the pipe that temperature is 400 DEG C~450 DEG C
In formula stove, then calcining at constant temperature 0.5h~1h in temperature is 400 DEG C~450 DEG C of tube furnace, deposition has N-type half in conductive substrates
Conductor TiO2Film, barrier layer is served as, obtain barrier layer/conductive substrates.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Step 2 3. in
To step 2,2. middle temperature is that barrier layer solution is poured into 65 DEG C~80 DEG C of beaker, then the constant temperature in the case where temperature is 65 DEG C~80 DEG C
2h~3h is stood, conductive substrates are taken out after reaction, conductive substrates are cleaned 4 times~5 times using distilled water, reuse absolute ethyl alcohol
Conductive substrates are cleaned 4 times~5 times, finally dried up using nitrogen；Conductive substrates are put into the pipe that temperature is 500 DEG C~650 DEG C
In formula stove, then calcining at constant temperature 1h~2h in temperature is 500 DEG C~650 DEG C of tube furnace, deposition has N-type partly to lead in conductive substrates
Body TiO2Film, barrier layer is served as, obtain barrier layer/conductive substrates.Other steps are identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Step 3 2. in
The concentration of butyl titanate is 45mmol/L~50mmol/L in described reaction solution I.Other steps and embodiment one
It is identical to seven.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：Step 3 3. in
The stop aspect of barrier layer/conductive substrates is tilted and is fixed in ptfe autoclave, into ptfe autoclave
Skeleton reaction solution is added, then ptfe autoclave is sealed；By the ptfe autoclave of sealing temperature be 150 DEG C
Heated at constant temperature 5h~8h at~180 DEG C, then cool to room temperature with the furnace；Temperature is put into after barrier layer/conductive substrates are taken out as 400
DEG C~450 DEG C of tube furnace in calcining at constant temperature 3h~4h, obtain homogeneity barrier layer/skeleton structure.Other steps and specific implementation
Mode one to eight is identical.
Embodiment ten：Present embodiment is homogeneity barrier layer/light of the skeleton structure as sensitization solar battery
Anode application.
Beneficial effects of the present invention are verified using following examples：
Contrast test one：Pure skeleton TiO2The preparation method of structure is completed according to the following steps：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 3 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtains clean conductive substrates；
Conductive substrates described in step 1 are FTO electro-conductive glass；
The frequency that conductive substrates are cleaned by ultrasonic in toluene in step 1 is 40kHz, and the time of ultrasonic cleaning is 20min,
The frequency that conductive substrates are cleaned by ultrasonic in acetone is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are in anhydrous second
The frequency being cleaned by ultrasonic in alcohol is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are cleaned by ultrasonic in deionized water
Frequency be 40kHz, the time of ultrasonic cleaning is 20min；
2nd, TiO is prepared with hydrothermal system2Skeleton：
1., into distilled water add mass fraction be 35% hydrochloric acid, stir, obtain hydrochloric acid solution；
Step 2 1. described in mass fraction be 35% hydrochloric acid and the volume ratio of distilled water be 1:1；
2., by step 2 1. in obtained hydrochloric acid solution be heated to 50 DEG C, then be 50 DEG C in temperature and mixing speed is
Butyl titanate is added dropwise under 50r/min, obtains reaction solution I；By the temperature control of reaction solution I at 50 DEG C, then temperature be 50 DEG C
It is to stir 1h under 50r/min with mixing speed, then naturally cools to room temperature, obtains skeleton reaction solution；
Step 2 2. described in reaction solution I in the concentration of butyl titanate be 50mmol/L；
3., the conducting surfaces of clean conductive substrates tilted be fixed in ptfe autoclave, to polytetrafluoroethylene (PTFE)
Skeleton reaction solution is added in reactor, then ptfe autoclave is sealed；By the ptfe autoclave of sealing in temperature
Spend for heated at constant temperature 5h at 180 DEG C, then cool to room temperature with the furnace；The pipe that temperature is 450 DEG C is put into after barrier layer/substrate is taken out
Calcining at constant temperature 3h in formula stove, obtain homogeneity barrier layer/skeleton structure；
Step 2 3. described in skeleton reaction solution volume and ptfe autoclave volumetric ratio be 0.75:1.
Contrast test two：The preparation method of pure barrier layer structure is completed according to the following steps：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 3 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtains clean conductive substrates；
Conductive substrates described in step 1 are FTO electro-conductive glass；
The frequency that conductive substrates are cleaned by ultrasonic in toluene in step 1 is 40kHz, and the time of ultrasonic cleaning is 20min,
The frequency that conductive substrates are cleaned by ultrasonic in acetone is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are in anhydrous second
The frequency being cleaned by ultrasonic in alcohol is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are cleaned by ultrasonic in deionized water
Frequency be 40kHz, the time of ultrasonic cleaning is 20min；
2nd, TiCl is utilized4Hydrolysis prepares barrier layer：
1., compound concentration is 20mmol/L titanium tetrachloride aqueous solution under ice-water bath, under ice-water bath and stirred after sealing
Speed is mixed to stir 1h under 50r/min, obtains barrier layer solution；
2., the conducting surface of clean conductive substrates be downwardly inclined be fixed in beaker, then by beaker in temperature be 70 DEG C
Lower constant temperature 1h；
3., to step 2,2. middle temperature is that barrier layer solution is poured into 70 DEG C of beaker, then constant temperature at being 70 DEG C in temperature
2h is stood, conductive substrates are taken out after reaction, conductive substrates are cleaned 4 times using distilled water, reuse absolute ethyl alcohol to conductive base
Bottom is cleaned 4 times, is finally dried up using nitrogen；Conductive substrates are put into temperature is in 450 DEG C of tube furnace, then in temperature is 450
DEG C tube furnace in calcining at constant temperature 0.5h, deposition has N-type semiconductor TiO in conductive substrates2Film, barrier layer is served as, obtained pure
Barrier layer structure；
Step 2 3. described in barrier layer solution volume and beaker volumetric ratio be 0.75:1.
Contrast test three：The method that one kind first prepares preparation barrier layer (S-BL) light anode structure after skeleton, is specifically pressed
What following steps were completed：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 3 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtains clean conductive substrates；
Conductive substrates described in step 1 are FTO electro-conductive glass；
The frequency that conductive substrates are cleaned by ultrasonic in toluene in step 1 is 40kHz, and the time of ultrasonic cleaning is 20min,
The frequency that conductive substrates are cleaned by ultrasonic in acetone is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are in anhydrous second
The frequency being cleaned by ultrasonic in alcohol is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are cleaned by ultrasonic in deionized water
Frequency be 40kHz, the time of ultrasonic cleaning is 20min；
2nd, TiO is prepared with hydrothermal system2Skeleton：
1., into distilled water add mass fraction be 35% hydrochloric acid, stir, obtain hydrochloric acid solution；
Step 2 1. described in mass fraction be 35% hydrochloric acid and the volume ratio of distilled water be 1:1；
2., by step 2 1. in obtained hydrochloric acid solution be heated to 50 DEG C, then be 50 DEG C in temperature and mixing speed is
Butyl titanate is added dropwise under 50r/min, obtains reaction solution I；By the temperature control of reaction solution I at 50 DEG C, then temperature be 50 DEG C
It is to stir 1h under 50r/min with mixing speed, then naturally cools to room temperature, obtains skeleton reaction solution；
Step 2 2. described in reaction solution I in the concentration of butyl titanate be 50mmol/L；
3., the conducting surfaces of clean conductive substrates tilted be fixed in ptfe autoclave, to polytetrafluoroethylene (PTFE)
Skeleton reaction solution is added in reactor, then ptfe autoclave is sealed；By the ptfe autoclave of sealing in temperature
Spend for heated at constant temperature 5h at 180 DEG C, then cool to room temperature with the furnace；Deimpurity conductive substrates will be gone to be put into temperature after taking out be
Calcining at constant temperature 3h in 450 DEG C of tube furnace, obtains skeleton structure/substrate；
Step 2 3. described in skeleton reaction solution volume and ptfe autoclave volumetric ratio be 0.75:1；
3rd, TiCl is utilized4Hydrolysis prepares barrier layer：
1., compound concentration is 20mmol/L titanium tetrachloride aqueous solution under ice-water bath, under ice-water bath and stirred after sealing
Speed is mixed to stir 1h under 50r/min, obtains barrier layer solution；
2., by the skeleton structure of skeleton structure/substrate down tilt be fixed in beaker, then by beaker temperature be 70
Constant temperature 1h at DEG C；
3., to step 3,2. middle temperature is that barrier layer solution is poured into 70 DEG C of beaker, then constant temperature at being 70 DEG C in temperature
2h is stood, skeleton structure/substrate is taken out after reaction, skeleton structure/substrate is cleaned 4 times using distilled water, reuses anhydrous second
Alcohol cleans 4 times to skeleton structure/substrate, is finally dried up using nitrogen；Skeleton structure/substrate is put into the pipe that temperature is 450 DEG C
In formula stove, then the calcining at constant temperature 0.5h in temperature is 450 DEG C of tube furnace, deposition has N-type semiconductor in skeleton structure/substrate
TiO2Film, serves as barrier layer, is first prepared the S-BL light anode structures on preparation barrier layer after skeleton；
Step 3 3. described in barrier layer solution volume and beaker volumetric ratio be 0.75:1.
Embodiment one：A kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis, specifically press with
What lower step was completed：
First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reused anhydrous
Alcohol flushing 3 times, is finally dried up using nitrogen, removes the greasy dirt on surface, obtains clean conductive substrates；
Conductive substrates described in step 1 are FTO electro-conductive glass；
The frequency that conductive substrates are cleaned by ultrasonic in toluene in step 1 is 40kHz, and the time of ultrasonic cleaning is 20min,
The frequency that conductive substrates are cleaned by ultrasonic in acetone is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are in anhydrous second
The frequency being cleaned by ultrasonic in alcohol is 40kHz, and the time of ultrasonic cleaning is 20min, and conductive substrates are cleaned by ultrasonic in deionized water
Frequency be 40kHz, the time of ultrasonic cleaning is 20min；
2nd, TiCl is utilized4Hydrolysis prepares barrier layer：
1., compound concentration is 20mmol/L titanium tetrachloride aqueous solution under ice-water bath, under ice-water bath and stirred after sealing
Speed is mixed to stir 1h under 50r/min, obtains barrier layer solution；
2., the conducting surface of clean conductive substrates be downwardly inclined be fixed in beaker, then by beaker in temperature be 70 DEG C
Lower constant temperature 1h；
3., to step 2,2. middle temperature is that barrier layer solution is poured into 70 DEG C of beaker, then constant temperature at being 70 DEG C in temperature
2h is stood, conductive substrates are taken out after reaction, conductive substrates are cleaned 4 times using distilled water, reuse absolute ethyl alcohol to conductive base
Bottom is cleaned 4 times, is finally dried up using nitrogen；Conductive substrates are put into temperature is in 450 DEG C of tube furnace, then in temperature is 450
DEG C tube furnace in calcining at constant temperature 0.5h, deposition has N-type semiconductor TiO in conductive substrates2Film, barrier layer is served as, hindered
Barrier/conductive substrates；
Step 2 3. described in barrier layer solution volume and beaker volumetric ratio be 0.75:1；
3rd, TiO is prepared with hydrothermal system2Skeleton：
1., into distilled water add mass fraction be 35% hydrochloric acid, stir, obtain hydrochloric acid solution；
Step 3 1. described in mass fraction be 35% hydrochloric acid and the volume ratio of distilled water be 1:1；
2., by step 3 1. in obtained hydrochloric acid solution be heated to 50 DEG C, then be 50 DEG C in temperature and mixing speed is
Butyl titanate is added dropwise under 50r/min, obtains reaction solution I；By the temperature control of reaction solution I at 50 DEG C, then temperature be 50 DEG C
It is to stir 1h under 50r/min with mixing speed, then naturally cools to room temperature, obtains skeleton reaction solution；
Step 3 2. described in reaction solution I in the concentration of butyl titanate be 50mmol/L；
3., the stop aspects of barrier layer/conductive substrates tilted be fixed in ptfe autoclave, to polytetrafluoroethyl-ne
Skeleton reaction solution is added in alkene reaction kettle, then ptfe autoclave is sealed；The ptfe autoclave of sealing is existed
Temperature is heated at constant temperature 5h at 180 DEG C, then cools to room temperature with the furnace；Temperature is put into after barrier layer/conductive substrates are taken out as 450
DEG C tube furnace in calcining at constant temperature 3h, obtain homogeneity barrier layer/skeleton structure；
Step 3 3. described in skeleton reaction solution volume and ptfe autoclave volumetric ratio be 0.75:1.
Embodiment two：The present embodiment and the difference of embodiment one are：Step 2 1. under ice-water bath compound concentration be
60mmol/L titanium tetrachloride aqueous solution, after sealing under ice-water bath and mixing speed be 50r/min under stir 1h, stopped
Layer solution.Other steps and parameter and all same of embodiment one.
Fig. 1 is the SEM figures on barrier layer in barrier layer/conductive substrates prepared by the step 2 of embodiment one；
From fig. 1, it can be seen that the smooth densification of barrier layer surface prepared by the step 2 of embodiment one, covering is uniform.
Fig. 2 is that the section SEM of barrier layer and substrate schemes in barrier layer/substrate prepared by the step 2 of embodiment one；
It can be observed from fig. 2 that barrier layer thickness prepared by chemical bath deposition is controllable, and uniform compact, the step 2 of embodiment one
The barrier layer thickness of preparation about 350nm.
Fig. 3 is UV-permeable spectrogram, in Fig. 31 be glass base the UV-permeable curve of spectrum, 2 be the ultraviolet of FTO
The curve of spectrum is crossed, 3 be the UV-permeable curve of spectrum of the barrier layer/conductive substrates prepared in the step 2 of embodiment one, and 4 be implementation
The UV-permeable curve of spectrum of the barrier layer/conductive substrates prepared in the step 2 of example two；
As can be seen from Figure 3, the barrier layer light transmittance that prepared by chemical bath deposition is high, and the light utilization efficiency of battery is high, it is seen that light region
Light transmittance is more than 70%.
Fig. 4 is the SEM figures of 3. homogeneity barrier layer/skeleton structure that the step 3 of embodiment one is prepared；
As can be seen from Figure 4, the TiO of growth2Nanowire length is homogeneous, and arrangement is fine and close, bundled shape structure, quantum dot adsorbance
Greatly.
Fig. 5 is the section SEM figures of 3. homogeneity barrier layer/skeleton structure that the step 3 of embodiment one is prepared；
As can be seen from Figure 5, first prepare and prepare behind barrier layer in light anode structure prepared by the order of skeleton, skeleton thickness is about
2.7 μm, barrier layer thickness is homogeneous, about 350nm.
Fig. 6 is the SEM figures of S-BL light anode structures prepared by contrast test three；
As can be seen from Figure 6, first prepare and prepare after skeleton in the light anode structure that the preparation order on barrier layer obtains, TiO2Nanometer
One layer of membrane structure of line skeleton structure Surface coating, destroys the energy of adsorption that skeleton structure is distributed and reduced quantum dot in order
Power, electrolyte enters skeleton structure difficulty after being assembled into battery.
Fig. 7 is the section SEM figures of S-BL light anode structures prepared by contrast test three；
As can be seen from Figure 7, first prepare and prepare after skeleton in the light anode structure that the preparation order on barrier layer obtains, without obvious
Skeleton/stop bed boundary, skeleton because deposition stop layer height increased, press close to the compact area uneven thickness of conductive substrates
It is even, it is difficult to ensure barrier deposition effect.
Fig. 8 is X ray diffracting spectrum, and 1 is FTO main components SnO in Fig. 82Standard X-ray diffraction collection of illustrative plates, 2 be golden red
The standard X-ray diffraction collection of illustrative plates of stone, 3 be the X ray diffracting spectrum of pure barrier layer structure prepared by contrast test two, and 4 be contrast
S-BL light anode structure X ray diffracting spectrums prepared by experiment three, the 5 homogeneity barrier layers 3. prepared for the step 3 of embodiment one/
The X ray diffracting spectrum of skeleton structure, " △ " are SnO2, " " is rutile；
As it can be observed in the picture that the barrier layer and skeleton structure that are prepared by chemical bath deposition are the Rutile Type TiO of homogeneity2
Structure.
The quantum dot sensitized solar cell experiment (one) of assembled inorganic：
First, prepare it is quantum dot sensitized after composite film：
1., homogeneity barrier layer/skeleton structure for first preparing embodiment one it is molten in the cadmium acetate that concentration is 0.1mol/L
1min is soaked in liquid, is immersed in Na after taking-up again21min is soaked in S methanol aqueous solution, 5 are rinsed using methanol after finally taking out
It is secondary, reuse nitrogen drying；
Step 1 1. described in Na2S methanol aqueous solution is by Na2S, methanol and distilled water mix, Na2S methanol
The volume ratio of methanol and distilled water is 1 in the aqueous solution:1；
2., repeat step 15 times, obtain the light anode of Surface coating CdS nanocrystals；
3., the light anodes of Surface coating CdS nanocrystals dried, then be immersed in 0.1mol/L zinc acetate solution and soak
5min is steeped, Na is immersed in after taking-up25min is soaked in the S aqueous solution, obtains coating one layer of ZnS light anode, reuses nitrogen and blow
It is dry, obtain it is quantum dot sensitized after composite film；
2nd, S is prepared2-/S/SO3 2-More sulphur electrolyte：
By Na2S, sublimed sulfur and sodium sulfite are dissolved in ethanol water, filtering solution impurity, S2-/S/SO3 2-More sulphur
Electrolyte；
S described in step 22-/S/SO3 2-Na in more sulphur electrolyte2S concentration is 2mol/L, and S concentration is 2mol/
L, Na2SO3Concentration be 0.2mol/L；
Ethanol water described in step 2 is mixed by absolute ethyl alcohol and distilled water, absolute ethyl alcohol and distilled water
Volume ratio is 7:3；
3rd, the composite film after will be quantum dot sensitized is as light anode, Cu2S is as cathode material, the brass of surface-brightening
For cathode material substrate, S2-/S/SO3 2-As reaction solution, control response area enters in 2mm × 2mm more sulphur electrolyte to battery
Row encapsulation, obtains inorganic-quantum-dot sensitization solar battery.
The quantum dot sensitized solar cell experiment (two) of assembled inorganic：This experiment and assembled inorganic it is quantum dot sensitized too
The difference of positive energy battery testing (one) is：Step 1 1. in the pure skeleton TiO that first prepares contrast test one2Structure is dense
Spend in the acetic acid cadmium solution for 0.1mol/L and soak 1min, be immersed in Na after taking-up again21min is soaked in S methanol aqueous solution,
Rinsed 5 times using methanol after finally taking out, reuse nitrogen drying；
Step 1 1. described in Na2S methanol aqueous solution is by Na2S, methanol and distilled water mix, Na2S methanol
The volume ratio of methanol and distilled water is 1 in the aqueous solution:1.The quantum dot sensitized solar energy of other steps and parameter and assembled inorganic
Battery testing (one) all same.
The quantum dot sensitized solar cell experiment (three) of assembled inorganic：This experiment and assembled inorganic it is quantum dot sensitized too
The difference of positive energy battery testing (one) is：Step 1 1. in the pure barrier layer structure that first prepares contrast test two in concentration
To soak 1min in 0.1mol/L acetic acid cadmium solution, Na is immersed in after taking-up again21min is soaked in S methanol aqueous solution, most
Rinsed 5 times using methanol after taking out afterwards, reuse nitrogen drying；
Step 1 1. described in Na2S methanol aqueous solution is by Na2S, methanol and distilled water mix, Na2S methanol
The volume ratio of methanol and distilled water is 1 in the aqueous solution:1.The quantum dot sensitized solar energy of other steps and parameter and assembled inorganic
Battery testing (one) all same.
The quantum dot sensitized solar cell experiment (four) of assembled inorganic：This experiment and assembled inorganic it is quantum dot sensitized too
The difference of positive energy battery testing (one) is：Step 1 1. in first prepare prepared by contrast test three to prepare after skeleton and hinder first
Barrier (S-BL) light anode structure soaks 1min in the acetic acid cadmium solution that concentration is 0.1mol/L, is immersed in Na after taking-up again2S
Methanol aqueous solution in soak 1min, finally take out after using methanol rinse 5 times, reuse nitrogen drying；
Step 1 1. described in Na2S methanol aqueous solution is by Na2S, methanol and distilled water mix, Na2S methanol
The volume ratio of methanol and distilled water is 1 in the aqueous solution:1.The quantum dot sensitized solar energy of other steps and parameter and assembled inorganic
Battery testing (one) all same.
Fig. 9 is the current density voltage curve of inorganic quantum dot sensitized solar cell, and 1 is assembled inorganic in Fig. 9
The Current density-voltage of the inorganic quantum dot sensitized solar cell of quantum dot sensitized solar cell experiment (one) assembling is bent
Line, the 2 inorganic quantum dot sensitized solar cells assembled for the quantum dot sensitized solar cell experiment (two) of assembled inorganic
Current density voltage curve, 3 for assembled inorganic quantum dot sensitized solar cell test (three) assembling inorganic quantum
The current density voltage curve of point sensitization solar battery, 4 test (four) for the quantum dot sensitized solar cell of assembled inorganic
The current density voltage curve of the inorganic quantum dot sensitized solar cell of assembling.
When external voltage is 0V, battery current now is short circuit current Jsc；When battery current is 0mA, now external voltage
It is worth, battery open circuit voltage V equal with battery open circuit voltage absolute valueoc=external voltage V (value).
The fill factor, curve factor FF=maximum battery powers P of batterymax/(Voc×Jsc), electricity conversion PCE=Pmax/Pin,
Wherein, Pin- simulated solar irradiation light source frequency；All photoelectric properties tests of the present invention are all with standard 1.5GHz 100mW/cm2Make
For analog light source, i.e. Pin=100mW/cm2；J in table 1sc(mA/cm2)、Voc(V), FF and PCE (%) is the data warp in Fig. 9
Above-mentioned formula analysis is calculated.
Table 1 tests (one), the quantum dot sensitized sun of assembled inorganic for the quantum dot sensitized solar cell of assembled inorganic
Can battery testing (two), assembled inorganic quantum dot sensitized solar cell experiment (three) and assembled inorganic it is quantum dot sensitized too
The photoelectric properties of the inorganic quantum dot sensitized solar cell of positive energy battery testing (four) assembling.
Table 1
Light anode prepared by barrier layer (S-BL) is prepared after skeleton and prepare after first preparing barrier layer to more first prepare
The contribution (C%) that light anode prepared by skeleton (BL-S) is lifted for battery efficiency, C%=(PCEx﹣ PCES)/PCEx× 100%
(the S-BL light anode structures that the homogeneity barrier layer/skeleton structure or contrast test three that x is prepared for embodiment one obtain, PCES
The electricity conversion of the pure barrier layer structure prepared for contrast test two)；
PCEBL-SThe electricity conversion of the homogeneity barrier layer/skeleton structure prepared for embodiment one；PCES-BLFor to having a competition
Test the electricity conversion of three obtained S-BL light anode structures；
Homogeneity barrier layer/skeleton structure prepared by embodiment one as light anode prepare it is inorganic it is quantum dot sensitized too
It is positive can battery with using the S-BL light anodes structure that contrast test three obtains as light anode prepare it is inorganic it is quantum dot sensitized too
Positive energy battery and the inorganic quantum dot sensitized sun for preparing pure barrier layer structure prepared by contrast test two as light anode
Energy battery is compared, and improved efficiency has contributed much, CBL-S%=813%, CS-BL%=347%, it is known that the homogeneity of preparation stops
Lifting of the first barrier layer back skeleton preparation order for battery performance has very great help in layer/skeleton.
Claims (10)
- A kind of 1. method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis, it is characterised in that one kind utilizes four What the method that titanium chloride hydrolysis prepares homogeneity barrier layer/skeleton structure was specifically realized by the following steps：First, conductive substrates are cleaned by ultrasonic in toluene, acetone, absolute ethyl alcohol and deionized water successively, reuse absolute ethyl alcohol Rinse 2 times~4 times, finally dried up using nitrogen, remove the greasy dirt on surface, obtain clean conductive substrates；2nd, TiCl is utilized4Hydrolysis prepares barrier layer：1., under ice-water bath compound concentration be 20mmol/L~60mmol/L titanium tetrachloride aqueous solution, in ice-water bath after sealing Lower and mixing speed is that 1h~3h is stirred under 50r/min~80r/min, obtains barrier layer solution；2., the conducting surface of clean conductive substrates be downwardly inclined be fixed in beaker, then by beaker in temperature be 50 DEG C~80 Constant temperature 0.5h~2h at DEG C；3., to step 2,2. middle temperature is that barrier layer solution is poured into 50 DEG C~80 DEG C of beaker, then in temperature be 50 DEG C~80 Constant temperature stands 1h~3h at DEG C, and conductive substrates are taken out after reaction, and conductive substrates are cleaned 3 times~5 times using distilled water, reused Absolute ethyl alcohol cleans 3 times~5 times to conductive substrates, is finally dried up using nitrogen；By conductive substrates be put into temperature for 400 DEG C~ In 650 DEG C of tube furnace, then calcining at constant temperature 0.5h~2h in temperature is 400 DEG C~650 DEG C of tube furnace, sunk in conductive substrates Product has N-type semiconductor TiO2Film, barrier layer is served as, obtain barrier layer/conductive substrates；Step 2 3. described in the volume of barrier layer solution and the volumetric ratio of beaker be (0.6~0.75):1；3rd, TiO is prepared with hydrothermal system2Skeleton：1., into distilled water add mass fraction be 32%~35% hydrochloric acid, stir, obtain hydrochloric acid solution；Step 3 1. described in mass fraction be 32%~35% hydrochloric acid and the volume ratio of distilled water be (0.8~2.3):1；2., by step 3 1. in obtained hydrochloric acid solution be heated to 40 DEG C~70 DEG C, then in temperature be 40 DEG C~70 DEG C and stirring Speed is that butyl titanate is added dropwise under 50r/min~80r/min, obtains reaction solution I；By the temperature control of reaction solution I at 40 DEG C ~70 DEG C, then 1h~3h is stirred in the case where temperature is 40 DEG C~70 DEG C and mixing speed is 50r/min~80r/min, then it is naturally cold But to room temperature, skeleton reaction solution is obtained；Step 3 2. described in reaction solution I in the concentration of butyl titanate be 45mmol/L~60mmol/L；3., the stop aspects of barrier layer/conductive substrates tilted be fixed in ptfe autoclave, it is anti-to polytetrafluoroethylene (PTFE) Addition skeleton reaction solution in kettle is answered, then ptfe autoclave is sealed；By the ptfe autoclave of sealing in temperature For heated at constant temperature 5h~10h at 150 DEG C~200 DEG C, then cool to room temperature with the furnace；It is put into after barrier layer/conductive substrates are taken out Calcining at constant temperature 3h~5h in the tube furnace that temperature is 400 DEG C~650 DEG C, obtains homogeneity barrier layer/skeleton structure；Step 3 3. described in the volume of skeleton reaction solution and the volumetric ratio of ptfe autoclave be (0.6~0.75): 1。
- 2. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its It is FTO electro-conductive glass, ITO electro-conductive glass or Flexible graphene substrate to be characterised by the conductive substrates described in step 1.
- 3. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its It is characterised by that the frequency that conductive substrates are cleaned by ultrasonic in toluene in step 1 is 30kHz~90kHz, the time of ultrasonic cleaning is 15min~60min, the frequency that conductive substrates are cleaned by ultrasonic in acetone are 30kHz~90kHz, and the time of ultrasonic cleaning is 15min~60min, the frequency that conductive substrates are cleaned by ultrasonic in absolute ethyl alcohol are 30kHz~90kHz, the time of ultrasonic cleaning For 15min~60min, the frequency that conductive substrates are cleaned by ultrasonic in deionized water is 30kHz~90kHz, ultrasonic cleaning when Between be 15min~60min.
- 4. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its Compound concentration is 20mmol/L~30mmol/L titanium tetrachloride aqueous solution under ice-water bath in being characterised by step 2 1., is sealed It is afterwards that 1h~2h is stirred under 50r/min~80r/min with mixing speed under ice-water bath, obtains barrier layer solution.
- 5. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its Compound concentration is 40mmol/L~60mmol/L titanium tetrachloride aqueous solution under ice-water bath in being characterised by step 2 1., is sealed It is afterwards that 1h~1.5h is stirred under 50r/min~80r/min with mixing speed under ice-water bath, obtains barrier layer solution.
- 6. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its To step 2,2. middle temperature is to pour into barrier layer solution in 50 DEG C~65 DEG C of beaker in being characterised by step 2 3., then in temperature Stand 1h~2h for constant temperature at 50 DEG C~65 DEG C, conductive substrates taken out after reaction, conductive substrates are cleaned using distilled water 3 times~ 4 times, reuse absolute ethyl alcohol and conductive substrates are cleaned 3 times~4 times, finally dried up using nitrogen；Conductive substrates are put into temperature For in 400 DEG C~450 DEG C of tube furnaces, then calcining at constant temperature 0.5h~1h in the tube furnace that temperature is 400 DEG C~450 DEG C, lead Deposition has N-type semiconductor TiO in electric substrate2Film, barrier layer is served as, obtain barrier layer/conductive substrates.
- 7. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its To step 2,2. middle temperature is to pour into barrier layer solution in 65 DEG C~80 DEG C of beaker in being characterised by step 2 3., then in temperature Stand 2h~3h for constant temperature at 65 DEG C~80 DEG C, conductive substrates taken out after reaction, conductive substrates are cleaned using distilled water 4 times~ 5 times, reuse absolute ethyl alcohol and conductive substrates are cleaned 4 times~5 times, finally dried up using nitrogen；Conductive substrates are put into temperature For in 500 DEG C~650 DEG C of tube furnaces, then calcining at constant temperature 1h~2h in the tube furnace that temperature is 500 DEG C~650 DEG C, it is conductive Deposition has N-type semiconductor TiO in substrate2Film, barrier layer is served as, obtain barrier layer/conductive substrates.
- 8. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its The concentration of butyl titanate is 45mmol/L~50mmol/L in reaction solution I described in being characterised by step 3 2..
- 9. a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis according to claim 1, its The stop aspect of barrier layer/conductive substrates is tilted in being characterised by step 3 3. and is fixed in ptfe autoclave, to Skeleton reaction solution is added in ptfe autoclave, then ptfe autoclave is sealed；By the polytetrafluoroethylene (PTFE) of sealing Heated at constant temperature 5h~8h at reactor is 150 DEG C~180 DEG C in temperature, then cool to room temperature with the furnace；By barrier layer/conductive substrates Calcining at constant temperature 3h~4h in the tube furnace that temperature is 400 DEG C~450 DEG C is put into after taking-up, obtains homogeneity barrier layer/skeleton structure.
- 10. utilize a kind of method that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis as claimed in claim 1 The application of homogeneity barrier layer/skeleton structure of preparation, it is characterised in that homogeneity barrier layer/skeleton structure is as sensitization solar electricity The light anode application in pond.
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