CN108258120A - A kind of perovskite solar cell inexpensively stablized and the photoelectrocatalysidevice device of driving - Google Patents
A kind of perovskite solar cell inexpensively stablized and the photoelectrocatalysidevice device of driving Download PDFInfo
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Abstract
A kind of perovskite solar cell inexpensively stablized and the photoelectrocatalysidevice device of driving, belong to technical field of solar batteries and photo-electrocatalytic technology field.Apparatus structure mainly includes the mesoporous perovskite solar cell of low temperature carbon electrode, photoelectrocatalysielectrode electrode, to electrode, photovoltaic reaction pond, stirring system.The mesoporous perovskite solar cell for making anode using low temperature carbon pastes provides voltage, and the electron hole of photoelectrocatalysielectrode electrode is promoted to detach, enhancing photoelectrocatalysis effect, the organic matter in fast degradation water body.Device and method are simple, have excellent performance, stablize, of low cost, and whole system is using solar energy as sole energy source, and economical and energy saving is environmentally protective.
Description
Technical field
The invention belongs to technical field of solar batteries and photo-electrocatalytic technology field, and in particular to a kind of inexpensively stabilization
The photoelectrocatalysidevice device of perovskite solar cell driving and application.
Background technology
With the development of economy and society, energy and environment problem is gradually taken seriously, mankind nowadays society faces fossil energy
Phenomena such as exhaustion in source, water pollution, atmosphere pollution, noxious waste pollution, is on the rise, and solves these problems and has compeled
The eyebrows and eyelashes.Photoelectric conversion technique based on semiconductor, simple for process because its is of low cost, reaction condition mildly waits remarkable advantages,
The attention of people is increasingly subject in energy and environment protection.This mesoporous perovskite battery of low temperature carbon electrode is passed without using hole
Defeated material, without evaporation metal electrode, material price and process costs are cheap, due to meso-hole structure be separated out it is multiple independent small
Space, the moisture resistance enhancing of perovskite, so the stability of battery gets a promotion.On the other hand, electrode is made in photochemical catalyst
For form compared with traditional powder photocatalytic, this electricity assisted photo-catalysis water technology possesses repeatable recycling, to environment friend
It is good, the compound of photo-generated carrier is inhibited to significantly increase light-catalysed effect by extra electric field.It is specifically described, battery is urged in photoelectricity
Polarizing electrode and apply certain voltage between electrode, light induced electron is driven to external circuit, to prevent answering for photo-generated carrier
It closes.Meanwhile using solar energy as lasting energy source, realize energy conservation and environmental protection truly.And traditional light
Applied voltage applied in electro-catalysis technology is not often to be directed to solar energy, is directly driven using solar energy whole
A device is realized completely by solar energy come degradable organic pollutant, is a completely new Research Thinking, for solving human society
Energy problem and environment difficulties in evolution have important theory significance and realistic meaning.Pass through photoelectrocatalysielectrode electrode
With solar battery group into cascaded structure, the electric energy provided with perovskite solar cell drives photocatalysis film, realizes
It is a kind of realistic plan completely by the photoelectrocatalysis of Driven by Solar Energy.
Invention content
The purpose of the present invention is to provide a kind of perovskite solar cell inexpensively stablized and the photoelectrocatalysis dresses of driving
It puts, the degradation applied to organic pollution.Device is economic and environment-friendly without additional power supply completely by Driven by Solar Energy.
Perovskite solar cell, which is characterized in that be the mesoporous perovskite solar cell of low temperature carbon electrode, from bottom to top
It is followed successively by FTO electro-conductive glass cathode, compacted zone titanium dioxide hole blocking layer, mesoporous TiO 2 electron transfer layer, mesoporous two
Zirconium oxide separation layer, carbon nano tube modified interface, carbon electrode positive electrode；It is filled in mesoporous ZrO 2 separation layer, carbon nanotube
Modify the methylamine lead iodide (MAPbI in interface gaps3) perovskite light absorbing layer.
0~100nm of thickness (not including 0, preferably 60nm) of compacted zone titanium dioxide hole blocking layer is advanced optimized, is situated between
100~300nm of thickness (preferably 200nm), the mesoporous ZrO 2 of porous titanium dioxide electron transfer layer make the thickness 100 of separation layer
~300nm (preferably 200nm), carbon nanotube support layer 0~200nm of thickness (not including 0, preferably 100nm), be filled in it is mesoporous
Methylamine lead iodide in titanic oxide electronic transport layer, mesoporous ZrO 2 separation layer, carbon nanotube support layer gap
(MAPbI3) perovskite light absorbing layer.
Further methylamine lead iodide (MAPbI3) perovskite light absorbing layer use methylamine (CH3NH2) gas modification, it is caused
Close even curface.
The preparation method of the mesoporous perovskite solar cell of low temperature carbon electrode includes the following steps：
(1) hole blocking layer is prepared, using the glass FTO of fluorine-doped tin oxide is coated with as electro-conductive glass substrate, successively
Using acetone, ultra-pure water, absolute ethyl alcohol supersound washing FTO electro-conductive glass, naturally dry, UV ozone processing is cooled to room temperature standby
With the butanol solution drops of, bis- (levulinic ketone group) diisopropyl titanate esters on clean FTO, carry out spin coating (3000~
Spin coating under the conditions of 10000rmp), then 100~125 DEG C of 5~10min of processing on hot plate, obtain fine and close TiO2Layer；
(2) mesoporous TiO 2 electron transfer layer is prepared, TiO is coated on compacted zone2Mesoporous layer, hydro-thermal method synthesis TiO2
Powder, according to TiO2Powder：Ethyl cellulose：The mass ratio (0.5~1.5) of terpinol：(4~8)：(2~5), preferably 1:6:
3, addition ethyl cellulose, terpinol etc. are prepared into TiO2Slurry, ball milling, according to TiO2Slurry：Ethyl alcohol volume ratio is 1:1~4 is dilute
The slurry drop released carries out spin coating (the preferably spin coating under the conditions of 3000~10000rmp), then in Muffle furnace on compacted zone
400~650 DEG C of calcinings, heating rate are 1~4 DEG C/min；
(3) zirconium dioxide separation layer, hydro-thermal method synthesis ZrO are prepared2Powder, according to ZrO2Powder：Ethyl cellulose：Pine tar
The mass ratio (0.5~1.5) of alcohol：(4~8)：(2~5), preferably 1:6:3, addition ethyl cellulose, terpinol etc. are prepared into
ZrO2Slurry, according to ZrO2Slurry：：Ethyl alcohol volume ratio is 1:1~4 diluted slurry drop is in mesoporous TiO 2 electron transfer layer
On, spin coating (the preferably spin coating under the conditions of 3000~10000rmp) is carried out, then 400~650 DEG C of calcinings in Muffle furnace, heating
Rate is 1~4 DEG C/min；
(4) carbon nanotube is dispersed in N, N- by the preparation of carbon nanotube support layer according to mass percent concentration 1~10%
Dimethylformamide (DMF), is then spin coated onto on zirconium dioxide separation layer, dried for standby；
(5) filling of perovskite and the preparation of carbon electrode, are synthesized by two-step process perovskite, and the first step is spin coating PbI2
Layer, by 0.5~1.5mol/L PbI2DMF (n,N-Dimethylformamide) solution be spun in carbon nanotube support layer, turn
Speed is 3000~10000rmp, 10~30s of time, then by film in PbI2In heating plate 70~100 DEG C annealing 10~
30min, film color become buff from light yellow；Second step is leaching CH3NH3The aqueous isopropanol of I, by above-mentioned PbI2Film
It is impregnated in the CH of 5~10mg/L3NH330~90s in I aqueous isopropanols, obtains MAPbI3Film, color are gradually become by yellow
Brown, dry to be placed in heating plate 70~100 DEG C of 10~30min of annealing, film color becomes dark-brown；Then carbon pastes pass through
Perovskite surface is screen printed onto, battery is finally placed in 70~100 DEG C of 10~30min of annealing in heating plate；
Or further (5) further include the modification of perovskite, and step (5) is prepared to the perovskite MAPbI completed3It is positioned over and fills
Full methylamine (CH3NH2) gas wide-mouth bottle in 1~10s, perovskite becomes colorless pellucidity, takes out wide-mouth bottle, perovskite is fast
Speed becomes brown and surface-brightening；Then the preparation of carbon electrode is carried out：Carbon pastes are by being screen printed onto perovskite surface, finally
Battery is placed in 90~100 DEG C of 10~30min of annealing in heating plate.
The present invention provides a kind of photoelectrocatalysidevice device of perovskite solar cell driving inexpensively stablized, and mainly includes：
The mesoporous perovskite solar cell of low temperature carbon electrode, photoelectrocatalysielectrode electrode, to electrode, photovoltaic reaction pond, stirring system.
The mesoporous perovskite solar cell anode connection photoelectrocatalysielectrode electrode of low temperature carbon electrode, the cathode of battery are connected to electricity
Pole, photoelectrocatalysielectrode electrode with to electrode while immersed in forming access, the electricity in photovoltaic reaction pond in the electrolyte in photovoltaic reaction pond
Solution liquid is in magnetic agitation system, and photovoltaic reaction pond is made of translucent material；
Photoelectricity extremely titanium dioxide electrodes (TiO2), vanadic acid bismuth pole (BiVO4), the compound electric of graphene and titanium dioxide
Pole (RGO/TiO2), the combination electrode (CNT/TiO of carbon nanotube and titanium dioxide2), the combination electrode of activated carbon and titanium dioxide
(AC/TiO2), preferably carbon nanotube and the compound electrode of titanium dioxide.It is to electrode, platinum electrode, carbon electrode, preferably platinum electrode.
Specific preparation method is as follows：0.1~5%wt carbon nanotubes add in titania powder, with terpinol and ethyl cellulose according to
(0.5~1.5)：(4~8)：(2~5), preferably 1:6:3 prepare slurry, and slurry is scratched on FTO electro-conductive glass, optoelectronic pole area
For 1~9cm2, burn 0.5~1.2h in 400~650 DEG C.The preferred 5mol/L sodium sulphate of electrolyte, the mesoporous perovskite of low temperature carbon electrode
The organic pollution of the photoelectrocatalysidevice device degradation of solar cell driving is rhodamine B.
Compared with prior art, the present invention has the following advantages：
1) method provided by the present invention is simple, has excellent performance, of low cost.
2) the mesoporous perovskite solar cell of low temperature carbon electrode provided by the present invention, using low temperature carbon pastes as electrode,
Without organic bath as hole transmission layer, without evaporation metal to electrode, of low cost, performance is stablized.
3) the mesoporous perovskite solar cell of low temperature carbon electrode provided by the present invention, by carbon nano tube modified separation layer
With the transport interface of carbon electrode, the efficiency of battery is improved significantly.
4) the mesoporous perovskite solar cell of low temperature carbon electrode provided by the present invention, on carbon nano tube modified basis
On, it is further modified with methylamine gas, perovskite surface becomes smooth, and efficiency further gets a promotion.
5) photoelectrocatalysidevice device of the mesoporous perovskite solar cell driving of low temperature carbon electrode provided by the present invention, can drop
Organic pollution is solved, energy source is solar energy, and device is recyclable, is reused.
6) photoelectrocatalysidevice device of the mesoporous perovskite solar cell driving of low temperature carbon electrode provided by the present invention, photoelectricity
Catalytic film is CNT/TiO2Composite material, photoelectrochemical degradation are efficient.
Description of the drawings
The mesoporous perovskite solar battery structure schematic diagram of low temperature carbon electrode in Fig. 1, embodiment.
The mesoporous perovskite solar battery structure scanning electron microscope (SEM) photograph of low temperature carbon electrode in Fig. 2, embodiment.
Perovskite flat scanning electron microscope in Fig. 3, embodiment 1.
Pass through carbon nano tube modified perovskite flat scanning electron microscope in Fig. 4, embodiment 2.
By carbon nanometer and the perovskite flat scanning electron microscope of the dual modification of methylamine gas in Fig. 5, embodiment 3.
The J-V performance maps of the mesoporous perovskite solar cell of low temperature carbon electrode in Fig. 6, embodiment.
The photoelectrocatalysidevice device structural representation of the mesoporous perovskite solar cell driving of low temperature carbon electrode in Fig. 7, embodiment 4
Figure.
To the degradation curve of rhodamine B in Fig. 8, embodiment 4.
1 carbon electrode, 2 carbon nano tube modified interfaces, 3 perovskites, 4 mesoporous ZrO 2 separation layers, 5 mesoporous TiO 2s electricity
Sub- transport layer, 6 fine and close titanium dioxide hole blocking layers, 7 FTO electro-conductive glass, 8 solar cells, 9 photovoltaic reaction ponds, 10 light
Electro catalytic electrode, 11 magnetic agitation systems, 12 pairs of electrodes.
Specific embodiment
With reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.Following reality
A carbon electrode area is applied as 0.07~4cm2。
Embodiment 1
As shown in Figure 1, the mesoporous perovskite solar battery structure schematic diagram of low temperature carbon electrode, carbon electrode 1 is as battery
Positive electrode, carbon nanotube 2 modify interface, and perovskite 3 is filled in mesoporous ZrO 2 as light absorbing layer and titanium dioxide is every
In one layer, wherein zirconium dioxide separation layer 4 separates carbon electrode 1 and titanic oxide electronic transport layer 5, and fine and close titanium dioxide makees 6
For hole blocking layer, cathode of the FTO electro-conductive glass 7 as battery, the mesoporous perovskite solar cell of low temperature carbon electrode it is complete
It is as shown in Figure 2 to tie scanning electron microscope (SEM) photograph.
The preparation of the mesoporous perovskite solar cell of low temperature carbon electrode：
(1) surface is coated with the glass FTO of fluorine-doped tin oxide as electro-conductive glass substrate, uses acetone, ultrapure successively
Water, absolute ethyl alcohol supersound washing FTO electro-conductive glass, then naturally dry irradiates 20min with UV ozone machine, to be cooled to room temperature
Afterwards, with the 80 μ L drops Tu of butanol solution of bis- (levulinic ketone group) the diisopropyl titanate esters of 0.15mol/L on clean FTO,
Spin coating 30s under the conditions of 3000rmp, then on hot plate 125 DEG C processing 5min.
(2) hydro-thermal method synthesis TiO2Powder, according to 1:6:3 addition ethyl celluloses, terpinol etc. are prepared into TiO2Slurry,
Ball milling 12h, according to 1:The 80 μ L drops of slurry of 4 diluted concentrations are on compacted zone, the spin coating 30s under the conditions of 5000rmp, then in horse
Not 500 DEG C of burning 30min in stove, heating rate are 2 DEG C/min.
(3) hydro-thermal method synthesis ZrO2Powder, according to 1:6:3 addition ethyl celluloses, terpinol etc. are prepared into ZrO2Slurry,
Ball milling 12h, with ethyl alcohol 1:TiO is coated in after 2 dilutions2Mesoporous layer, the spin coating 30s under the conditions of 5000rmp, then in Muffle furnace
500 DEG C of burning 30min, heating rate are 2 DEG C/min.
(4) the spin coating PbI in mesoporous shelf layer2Layer, by 1mol/L PbI2DMF (N,N-dimethylformamide) solution
40 μ L are spun on carbon nano tube modified mesoporous supporting layer, rotating speed 4000rmp, time 30s, then by film in PbI2Add
70 DEG C of annealing 30min, film color become buff from light yellow on hot plate.Second step is leaching CH3NH3The aqueous isopropanol of I,
By above-mentioned PbI2Film proofing is in the CH of 8mg/L3NH360s, MAPbI in I aqueous isopropanols3Film color is gradually become by yellow
Brown, dry to be placed in heating plate 90 DEG C of annealing 30min, film color becomes dark-brown, perovskite thin film scanning electron microscope such as Fig. 3
It is shown.
(5) battery is finally placed in 90 DEG C of annealing in heating plate by carbon pastes by being screen printed onto perovskite surface
30min。
Embodiment 2
In the present embodiment, step (1), (2), (3), (5) and with embodiment 1 identical (4) according to 3% mass fraction by carbon
Nanotube is dispersed in n,N-Dimethylformamide (DMF), and then 30s is spin-coated on ZrO under the conditions of 2000rmp2Separation layer, 100
DEG C annealing 30min, the spin coating PbI in mesoporous shelf layer2Layer, by 1mol/L PbI2DMF (N,N-dimethylformamide) solution
40 μ L are spun on carbon nano tube modified mesoporous supporting layer, rotating speed 4000rmp, time 30s, then by film in PbI2Add
70 DEG C of annealing 30min, film color become buff from light yellow on hot plate.Second step is leaching CH3NH3The aqueous isopropanol of I,
By above-mentioned PbI2Film proofing is in the CH of 8mg/L3NH360s, MAPbI in I aqueous isopropanols3Film color is gradually become by yellow
Brown, dry to be placed in heating plate 90 DEG C of annealing 30min, film color becomes dark-brown, perovskite thin film scanning electron microscope such as Fig. 4
It is shown.
Embodiment 3
In the present embodiment, step (1), (2), (3), (5) and identical with embodiment 1.
(4) carbon nanotube is dispersed in n,N-Dimethylformamide (DMF), Ran Hou according to 3% mass fraction
30s is spin-coated on ZrO under the conditions of 2000rmp2Separation layer, 100 DEG C of dry 30min, the spin coating PbI in mesoporous shelf layer2Layer, will
1mol/L PbI240 μ L of DMF (n,N-Dimethylformamide) solution be spun on carbon nano tube modified mesoporous supporting layer,
Rotating speed is 4000rmp, time 30s, then by film in PbI270 DEG C of annealing 30min in heating plate, film color is by light yellow
Become buff.Second step is leaching CH3NH3The aqueous isopropanol of I, by above-mentioned PbI2Film proofing is in the CH of 8mg/L3NH3I isopropyls
60s in alcoholic solution, MAPbI3Film color gradually becomes brown by yellow, dry to be placed in heating plate 90 DEG C of annealing 30min, thin
Film color becomes dark-brown, and the perovskite for preparing completion is positioned over full of methylamine (CH3NH2) gas wide-mouth bottle in 2-3s, calcium
Titanium ore becomes colorless pellucidity, takes out wide-mouth bottle, and perovskite rapidly goes to brown and surface-brightening.Perovskite thin film scanning electricity
Mirror is as shown in Figure 5.
The mesoporous perovskite solar energy of the low temperature carbon electrode by carbon nanotube and the dual modification of methylamine gas finally assembled
Battery, J-V performance maps are as shown in fig. 6, the short circuit current of monoblock battery is 20.49mAcm-2, open-circuit voltage 1.02V, filling
The factor is 44.5%.
Embodiment 4
The photoelectrocatalysidevice device that perovskite solar cell used in the present embodiment is connected with optoelectronic pole, battery portion be by
Carbon nanotube and the mesoporous perovskite solar cell of the low temperature carbon electrode of the dual modification of methylamine gas, same as Example 3, photoelectricity
Catalysis electrode is the compound (CNT/TiO of carbon nanotube and titanium dioxide2) membrane electrode, specific preparation method is as follows：0.75%
Wt carbon nanotubes add in titania powder, with terpinol and ethyl cellulose according to 1:6:3 prepare slurry, and slurry blade coating exists
On FTO electro-conductive glass, optoelectronic pole area is 4cm2, then 500 DEG C of burning 30min in Muffle furnace, heating rate are 2 DEG C/min.
Device is as shown in fig. 7, solar cell 8 provides bias, magnetic agitation system 11, the sun to reaction system in photovoltaic reaction pond 9
Energy anode connection photoelectrocatalysielectrode electrode 10, cathode are connected to electrode (platinum) 12.
Rhodamine B in photoelectric catalysis degrading water：Solar cell anode connects CNT/TiO2Film photoelectric electrode makees work electricity
Pole, optoelectronic pole area are 4cm2, cathode connection platinum is to electrode, and optoelectronic pole is with platinum to electrode while immersed in 0.5mol/L's
Na2SO4Two electrode systems are built in electrolyte.The rhodamine B of certain mass is dissolved into electrolyte, is configured to concentration
It is 0.5 × 10-5The target degradation product solution 50mL of mol/L, stirring make target degradation product reach on membrane electrode surface absorption-take off
Attached balance.Later, illumination, light source 160mW/cm are carried out to film and perovskite solar cell2Visible ray, pass through purple
The concentration variation of target degradation product in outside-visible spectrophotometer observation solution.
Under illumination condition, the voltage that solar cell provides is by CNT/TiO2The photo-generate electron-hole pair that film generates
In electric drive to electrode participate in reduction reaction, and with high oxidative capacity hole anode participate in oxidation reaction.Institute
State photoelectrocatalytioxidation oxidation system can in 1h to the degradation rate of rhodamine B close to 100% (such as Fig. 8), performance is substantially better than simple electricity
Catalysis and photocatalytic system.
The mesoporous perovskite solar cell of low temperature carbon electrode prepared using the present invention, will be to original mesoporous solar cell
Structure and performance optimization are carried out, the perovskite between separation layer and carbon electrode is repaiied by carbon nanotube, the electric current of battery significantly carries
It rises, efficiency significantly increases.The perovskite further obtained by methylamine processing two-step method, is that perovskite surface becomes smooth cause
It is close, increase the contact between carbon electrode and perovskite, finally improve its solar conversion efficiency.Photoelectrocatalysis prepared by the present invention
Electrode is CNT/TiO2Film, photoelectrocatalysis efficiency are better than simple TiO2Film, degradable organic pollutant it is with obvious effects.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (9)
1. perovskite solar cell, which is characterized in that for the mesoporous perovskite solar cell of low temperature carbon electrode, from bottom to top according to
Secondary is FTO electro-conductive glass cathode, compacted zone titanium dioxide hole blocking layer, mesoporous TiO 2 electron transfer layer, mesoporous dioxy
Change zirconium separation layer, carbon nano tube modified interface, carbon electrode positive electrode；It is filled in mesoporous ZrO 2 separation layer, carbon nanotube is repaiied
Adorn the methylamine lead iodide (MAPbI in interface gaps3) perovskite light absorbing layer.
2. perovskite solar cell described in accordance with the claim 1, which is characterized in that compacted zone titanium dioxide hole blocking layer
0~100nm of thickness (preferably 60nm), 100~300nm of thickness (preferably 200nm) of mesoporous TiO 2 electron transfer layer, be situated between
It is (excellent that hole zirconium dioxide makees 100~300nm of thickness (preferably 200nm) of separation layer, 0~200nm of thickness of carbon nanotube support layer
Select 100nm).
3. perovskite solar cell described in accordance with the claim 1, which is characterized in that be filled in mesoporous TiO 2 electronics biography
Methylamine lead iodide (MAPbI in defeated layer, mesoporous ZrO 2 separation layer, carbon nanotube support layer gap3) perovskite light absorption
Layer.
4. perovskite solar cell described in accordance with the claim 1, which is characterized in that methylamine lead iodide (MAPbI3) perovskite
Light absorbing layer also uses methylamine (CH3NH2) modified.
5. prepare the method for Claims 1 to 4 any one of them perovskite solar cell, which is characterized in that including following
Step：
(1) hole blocking layer is prepared, using the glass FTO for being coated with fluorine-doped tin oxide as electro-conductive glass substrate, is used successively
Acetone, ultra-pure water, absolute ethyl alcohol supersound washing FTO electro-conductive glass, naturally dry, UV ozone processing be cooled to room temperature it is spare,
The butanol solution drop of bis- (levulinic ketone group) diisopropyl titanate esters carries out spin coating, then in heating plate on clean FTO
5~10min of upper 100~125 DEG C of processing, obtains fine and close TiO2Layer；
(2) mesoporous TiO 2 electron transfer layer is prepared, TiO is coated on compacted zone2Mesoporous layer, hydro-thermal method synthesis TiO2Powder,
According to TiO2Powder：Ethyl cellulose：The mass ratio (0.5~1.5) of terpinol：(4~8)：(2~5), preferably 1:6:3, addition
Ethyl cellulose, terpinol etc. are prepared into TiO2Slurry, ball milling, according to TiO2Slurry：Ethyl alcohol volume ratio is 1:1~4 diluted slurry
Drop carries out spin coating (the preferably spin coating under the conditions of 3000~10000rmp) on compacted zone, then 400 in Muffle furnace~
650 DEG C of calcinings, heating rate are 1~4 DEG C/min；
(3) zirconium dioxide separation layer, hydro-thermal method synthesis ZrO are prepared2Powder, according to ZrO2Powder：Ethyl cellulose：Terpinol
Mass ratio (0.5~1.5)：(4~8)：(2~5), preferably 1:6:3, addition ethyl cellulose, terpinol etc. are prepared into ZrO2Slurry
Material, according to ZrO2Slurry：：Ethyl alcohol volume ratio is 1:1~4 diluted slurry drop on mesoporous TiO 2 electron transfer layer, into
Row spin coating, then 400~650 DEG C of calcinings in Muffle furnace, heating rate are 1~4 DEG C/min；
(4) carbon nanotube is dispersed in N, N- diformazans by the preparation of carbon nanotube support layer according to mass percent concentration 1~10%
Base formamide (DMF), is then spin coated onto on zirconium dioxide separation layer, dried for standby；
(5) filling of perovskite and the preparation of carbon electrode, are synthesized by two-step process perovskite, and the first step is spin coating PbI2Layer, will
0.5~1.5mol/L PbI2DMF (n,N-Dimethylformamide) solution be spun in carbon nanotube support layer, rotating speed is
3000~10000rmp, 10~30s of time, then by film in PbI270~100 DEG C of 10~30min that anneal, thin in heating plate
Film color becomes buff from light yellow；Second step is leaching CH3NH3The aqueous isopropanol of I, by above-mentioned PbI2It is thin film dipped in 5~
The CH of 10mg/L3NH330~90s in I aqueous isopropanols, obtains MAPbI3Film, color gradually become brown by yellow, after doing
It is placed in 70~100 DEG C of 10~30min of annealing, film color in heating plate and becomes dark-brown；Then carbon pastes pass through silk-screen printing
On perovskite surface, battery is finally placed in 70~100 DEG C of 10~30min of annealing in heating plate；
Or further (5) further include the modification of perovskite, and step (5) is prepared to the perovskite MAPbI completed3It is positioned over full of first
Amine (CH3NH2) gas wide-mouth bottle in 1~10s, perovskite becomes colorless pellucidity, takes out wide-mouth bottle, perovskite becomes rapidly
For brown and surface-brightening；Then the preparation of carbon electrode is carried out：Carbon pastes, finally will be electric by being screen printed onto perovskite surface
Pond is placed in 90~100 DEG C of 10~30min of annealing in heating plate.
6. the photoelectrocatalysidevice device of Claims 1 to 4 any one of them perovskite solar cell driving, which is characterized in that
Mainly include：The mesoporous perovskite solar cell of low temperature carbon electrode, photoelectrocatalysielectrode electrode are to electrode, photovoltaic reaction pond, stirring
System；
The mesoporous perovskite solar cell anode connection photoelectrocatalysielectrode electrode of low temperature carbon electrode, the cathode of battery are connected to electrode,
Photoelectrocatalysielectrode electrode with to electrode while immersed in forming access, the electrolyte in photovoltaic reaction pond in the electrolyte in photovoltaic reaction pond
In magnetic agitation system, photovoltaic reaction pond is made of translucent material.
7. according to the photoelectrocatalysidevice device described in claim 6, which is characterized in that photochemical catalyst electrode is selected from titanium dioxide electrodes
(TiO2), vanadic acid bismuth pole (BiVO4), the combination electrode (RGO/TiO of graphene and titanium dioxide2), carbon nanotube and titanium dioxide
Combination electrode (the CNT/TiO of titanium2), the combination electrode (AC/TiO of activated carbon and titanium dioxide2)。
8. according to the photoelectrocatalysidevice device described in claim 6, which is characterized in that be selected from platinum electrode, carbon electrode to electrode.
9. according to the photoelectrocatalysidevice device described in claim 6, which is characterized in that the specific preparation method of photochemical catalyst electrode is as follows：
0.1~5%wt carbon nanotubes add in titania powder, with terpinol and ethyl cellulose according to (0.5~1.5)：(4~8)：
(2~5), preferably 1:6:3 prepare slurry, and slurry is scratched on FTO electro-conductive glass, forms light optoelectronic pole, in 400~650 DEG C of burnings
0.5~1.2h.
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