CN109216548A - A kind of perovskite solar battery scrapes coating preparation method - Google Patents
A kind of perovskite solar battery scrapes coating preparation method Download PDFInfo
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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Abstract
What the present invention disclosed a kind of perovskite solar battery scrapes coating preparation method, comprising the following steps: prepares hole transmission layer, alumina layer, indium sulphur-perovskite composite layer, electron transfer layer in conductive substrates using knife coating, wherein the perovskite is CH3NH3PbI3；The aluminium oxide is by aluminium oxide: isopropanol: water: ethanol amine mixes by volume for 1:1-3:1-3:0.001-0.005；The present invention replaces traditional glass substrate using flexible substrates, realize the flexibility of perovskite solar battery, the range of perovskite solar cell application is widened, and preparation process is simple, it is low for equipment requirements, cost can be reduced using knife coating, realizes green production, without high temperature sintering, the mixture filming performance of indium sulphur and perovskite is good for the preparation of perovskite solar battery structure of the present invention simultaneously.
Description
Technical field
The present invention relates to the technical field of solar batteries based on the perovskite material of hybrid inorganic-organic, especially relate to
And a kind of perovskite solar battery scrapes coating preparation method.
Background technique
Perovskite solar battery (perovskitesolarcells) is due to being that dye-sensitized solar cells differentiation comes
A kind of novel solar battery；When receiving sunlight irradiation, calcium titanium ore bed absorbs photon first and generates electron-hole pair；By
In the difference of perovskite material exciton bind energy, these carriers perhaps become free carrier or form exciton；Then, this
A little not compound electrons and holes are collected by electron transfer layer and hole transmission layer respectively, i.e., electronics is transferred to electricity from calcium titanium ore bed
Sub- transport layer, is finally collected by conductive substrates；Hole is transferred to hole transmission layer from calcium titanium ore bed, is finally received by metal electrode
Collection.Perovskite solar battery is respectively glass conductive substrates (FTO), electron transfer layer (ETM), the suction of perovskite light from bottom to top
Receive layer (containing porous support), hole transmission layer (HTM) and back electrode.
In the conventional method, spin-coating method is still main stream approach, and this method can eaily obtain uniform calcium
Titanium ore film；But this process is very big to the loss of raw material, at high cost, rate is slow, is not suitable for large-scale industrial production.
In current technology, the preparation of calcium titanium ore bed and other main relevant functional layers is concentrated mainly on glove box
In, rely on inert gas shielding；This is a huge limitation for the volume production in perovskite future, and current techniques generally use
Glass conductive substrates, but substrate of glass brittleness is strong, can not be bent, and brings limitation to the preparation of later period functional layer, while also serious system
The about large-scale use of perovskite solar battery.
Summary of the invention
For the above-mentioned problems in the prior art, the present invention is intended to provide a kind of simply and effectively using blade coating legal system
The method of standby perovskite solar battery is mainly reflected in simpler efficient, low for equipment requirements, section in printing preparation method
About cost, and use method of the invention can efficiently prepare the perovskite solar battery of high quality in air.
In order to achieve the above object, the invention adopts the following technical scheme:
A kind of perovskite solar battery scrapes coating preparation method, comprising the following steps: is made in conductive substrates using knife coating
Standby hole transmission layer, alumina layer, indium sulphur-perovskite composite layer, electron transfer layer, wherein the perovskite is
CH3NH3PbI3；The aluminium oxide is by aluminium oxide: isopropanol: water: ethanol amine is 1:1-3:1-3:0.001-0.005 by volume
It mixes.
Using preparation method of the invention, hole transmission layer, alumina layer, copper and indium can be sequentially prepared in conductive substrates
Sulphur-perovskite composite layer and electron transfer layer, then prepare back electrode on the electron transport layer；It can also be using knife coating soft
Electron transfer layer, alumina layer, indium sulphur-indium sulphur-perovskite composite layer and hole transport are sequentially prepared in property conductive substrates
Layer, then prepares back electrode on the hole transport layer；Active layer of the invention is compound using indium sulphur-perovskite, and indium sulphur is received
Rice grain can be filled in indium sulphur-perovskite composite layer hole, the film forming of perovskite active layer be improved, to improve calcium
The photoelectric conversion efficiency of titanium ore solar battery；Aluminium oxide is by aluminium oxide: isopropanol: water: ethanol amine mixes according to a certain volume
Slurry can be scratched by being made, and can obtain suitable film forming thickness and the good uniformity, improve perovskite solar battery efficiency.
Preferably, the aluminium oxide is the aqueous dispersions of nano aluminium oxide, and the solid content of aluminium oxide is 20%~25%, is received
The partial size of rice aluminium oxide particles is 5nm~10nm；The nano aluminium oxide aqueous dispersions preferably are selected from Aladdin (Aladdin) product
The nano aluminium oxide aqueous dispersions of board.
As the optimal technical scheme of the method for the invention, the described method comprises the following steps:
S1, in conductive substrates scratch hole transmission layer precursor solution, then in 90 DEG C~100 DEG C annealing 10min~
15min, so that hole transmission layer be prepared in conductive substrates；
Wherein, blade coating speed is 20mm/s~25mm/s, and scraper height is 20 μm~50 μm；
S2, alumina slurry is scratched on the hole transport layer, then in 90 DEG C~100 DEG C annealing 10min~15min, thus
Alumina layer is prepared in conductive substrates；
Wherein, blade coating speed is 20mm/s~25mm/s, and scraper height is 35 μm~60 μm；
S3, on alumina layer scratch indium sulphur and perovskite mixed solution, then in 90 DEG C~100 DEG C annealing 10min~
20min, to obtain the compound indium sulphur of indium sulphur-perovskite-perovskite composite layer on alumina layer；
Wherein, blade coating speed is speed 15mm/s~20mm/s, and scraper height is 50 μm~80 μm；
S4, the solution that electron transfer layer is scratched on indium sulphur-perovskite composite layer, then in 90 DEG C~110 DEG C annealing 5min
~15min, to obtain electron transfer layer on indium sulphur-perovskite composite layer；
Wherein, blade coating speed is 18mm/s~25mm/s, and scraper height is 60 μm~90 μm.
Preferably, the hole transmission layer is CuInS2Layer, the CuInS2The preparation method of precursor solution is as follows:
Under nitrogen protection, the propionic acid of the indium acetate of every 0.08~0.12mmol, the thiocarbamide of 0.4~0.6mmol and 30~50 μ is dissolved into
In the butylamine of 0.4~0.8mL, and ultrasonic disperse is carried out, forms homogeneous solution, add the CuI of 0.09~0.13mmol, obtain
CuInS2Precursor solution.
Specifically, the area ratio of the volumetric usage and conductive substrates of the hole transmission layer solution be 15 μ L/ (2cm ×
4cm), under the conditions of this ratio, suitable film forming thickness and the good uniformity can be obtained.
It is furthermore preferred that the CuInS2Precursor solution further includes ethylene glycol, and the additive amount of the ethylene glycol is CuInS2Before
Drive the 5 ~ 10% of liquid solution total volume；Add the ethylene glycol of certain volume, adjustable CuInS2The viscosity of precursor solution, obtains
To slurry needed for present invention blade coating, be conducive to the film forming for improving hole transmission layer.
Preferably, the preparation method of the mixed solution of the indium sulphur and perovskite are as follows: by every 0.085~0.34mmol's
In(OAc)3, the CuI of 0.09~0.36mmol, the thiocarbamide of 0.043~0.17mmol be dissolved into the perovskite of 0.4~1.6mL
In n,N-Dimethylformamide solution, the mass percent of perovskite is in the n,N-Dimethylformamide solution of the perovskite
20~40%；On the one hand indium sulphur is added in perovskite can increase indium sulphur-perovskite composite layer film forming, another party
Face is conducive to improve the compactness of active layer, to improve the efficiency of perovskite solar battery.
Specifically, the 15 μ L/ (2cm × 4cm) of area ratio of the mixed solution and conductive substrates of indium sulphur and perovskite；?
Under the conditions of this ratio, suitable film forming thickness and the good uniformity can be obtained, with electron transfer layer or hole transmission layer
Contact is also more preferable.
Preferably, the electron transfer layer precursor solution be [6.6]-phenyl-C61- methyl butyrate PCBM and/or
[6.6]-phenyl-C71- methyl butyrate PCBM chlorobenzene solution；The concentration of the electron transfer layer precursor solution is 15mg/ml
~20mg/ml.
Specifically, the area ratio of the volumetric usage and conductive substrates of the electron transfer layer precursor solution is 20 μ L/
(2cm × 4cm) can obtain suitable film forming thickness and the good uniformity under the conditions of this ratio, with indium sulphur-calcium titanium
The contact of mine composite layer is also more preferable.
Preferably, further include preparing back electrode on the electron transport layer, obtain perovskite solar battery.
Preferably, the back electrode is the combination of any one or two kinds in metal electrode or carbon electrode.
Specifically, the mode for preparing back electrode on the electron transport layer is appointing in vapor deposition, silk-screen printing or printing
It anticipates one kind.
Preferably, the size of the conductive substrates is (2cm~10cm) × (2cm~10cm)；The conductive substrates are band
There is the transparent polymeric film of indium tin oxide ITO, in conjunction with doctor blade process, can obtain over a larger area more uniform
Film-forming region carries out subsequent step by choosing homogeneous film formation region, to improve obtained flexible perovskite solar battery
Performance.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention substitutes traditional glass substrate using the transparent polymeric film flexible substrates with ITO, is replaced with knife coating and is revolved
Coating is coated with all functional layers (hole transmission layer, alumina layer, indium sulphur-perovskite composite layer, electron transfer layer), passes through tune
The parameters such as blade coating speed and scraper height when the viscosity and blade coating of whole each functional layer slurry, can (air humidity exists in air
50 or less) the flexible perovskite solar battery that high quality is efficiently prepared in, prepares to be substituted in glove box, and operation is more
It is easy and cost is lower, while also reducing influence of the introducing of unfavorable factor to preparation method and properties of product；
(2) preparation of perovskite solar battery structure of the present invention is not necessarily to high temperature sintering, the mixture of indium sulphur and perovskite, copper
Indium sulphur nano particle can be filled in the hole of perovskite, the film forming of perovskite active layer be improved, to improve perovskite too
The photoelectric conversion efficiency of positive energy battery；
(3) aluminium oxide is by aluminium oxide: isopropanol: water: ethanol amine is mixed according to a certain volume can scratch slurry, in the present invention
Ratio under the conditions of, suitable film forming thickness and the good uniformity can be obtained, to improve perovskite solar battery
Efficiency；
(4) flexible perovskite solar battery preparation process of the invention is simple, low for equipment requirements, utilizes the advantage of knife coating
Save the cost to the full extent realizes green production；Replace traditional glass substrate using flexible substrates, realizes the perovskite sun
Can battery flexibility, widened the range of perovskite solar cell application, opened perovskite solar battery and march toward city
The gate of fieldization.
Detailed description of the invention
Fig. 1 is the i-v curve that sample prepared by embodiment 1 measures.
Fig. 2 is the i-v curve that sample prepared by embodiment 2 measures.
Fig. 3 is the i-v curve that sample prepared by embodiment 3 measures.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated；It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention；Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
The present invention will be further described With reference to embodiment.
Embodiment 1
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, specifically, is first coated on a flexible substrate
Hole transmission layer is then successively coated with alumina layer as mesoporous layer on the basis of hole transmission layer, and indium sulphur-perovskite is multiple
Layer is closed as photosensitive layer, then the coating electronic transport layer on indium sulphur-perovskite composite layer, finally uses the method for silk-screen printing
Brush one layer of silver paste.
A kind of perovskite solar battery scrapes coating preparation method, comprising the following steps:
S1, the precursor solution that 15 μ L hole transmission layers are scratched on flexible conducting substrate (2cm × 4cm), are then moved back in 100 DEG C
Fiery 10min, so that hole transmission layer be prepared on flexible conducting substrate；
Wherein, blade coating speed is 20mm/s, and scraper height is 20 μm；
The hole transmission layer is CuInS2Layer, the CuInS2The preparation method of precursor solution is as follows: by 0.1mmol acetic acid
Indium, 0.5mmol thiocarbamide and 40 μ L propionic acid are dissolved in 0.6mL butylamine, and are carried out ultrasonic disperse and formed it into homogeneous solution, then again
0.1mmol cuprous iodide is added in above-mentioned solution, and the ethylene glycol that overall solution volume 10% is added is uniformly mixed to get arriving
Hole transmission layer precursor solution；
S2,15 μ L alumina slurries are scratched on the hole transport layer, then in 100 DEG C of annealing 15min, thus in conductive substrates
Alumina layer is prepared；
Wherein, blade coating speed is 20mm/s, and scraper height is 40 μm；
The aluminium oxide is by Aladdin aluminium oxide aqueous dispersions: isopropanol: water: ethanol amine is 1:1.5:1.5 by volume:
0.001 mixes；
S3, the mixed solution that 15 μ L indium sulphurs and perovskite are scratched on alumina layer, then in 100 DEG C of annealing 15min, thus
Indium sulphur-perovskite composite layer is obtained on alumina layer；
Wherein, blade coating speed is speed 15mm/s, and scraper height is 60 μm；
The preparation method of the mixed solution of the indium sulphur and perovskite are as follows: by the In (OAc) of 0.17mmol3, 0.18mmol
The thiocarbamide of CuI and 0.085mmol is dissolved into (solvent N, N- dimethyl in the perovskite solution that 0.8mL mass fraction is 40%
Formamide)；
S4, the solution that 20 μ L electron transfer layers are scratched on indium sulphur-perovskite composite layer, then in 110 DEG C of annealing 5min, from
And electron transfer layer is obtained on indium sulphur-perovskite composite layer；
Wherein, blade coating speed is 25mm/s, and scraper height is 80 μm；
The electron transfer layer precursor solution is [6.6]-phenyl-C61- methyl butyrate PCBM and/or [6.6]-phenyl-C71-
The chlorobenzene solution of methyl butyrate PCBM；The concentration of the electron transfer layer precursor solution is 20mg/ml；
S5, one layer of silver paste is brushed using the method for silk-screen printing in sample surfaces, and makes its solidification at 100 DEG C.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, the electricity that is measured for it
Voltage curve is flowed, as shown in Figure 1；As shown in Figure 1, the open-circuit voltage 0.87V of solar cell sample, short circuit current 6.2mA are filled out
Fill the factor 0.35, efficiency 1.89%.
Embodiment 2
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In aluminium oxide described in step S2 is by Aladdin aluminium oxide aqueous dispersions: isopropanol: water: ethanol amine is 1:1:1 by volume:
0.003 mixes.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, the electricity that is measured for it
Voltage curve is flowed, as shown in Figure 2；As shown in Figure 2, the open-circuit voltage 0.86V of solar cell sample, short circuit current 4.8mA are filled out
Fill the factor 0.33, efficiency 1.36%.
Embodiment 3
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In aluminium oxide described in step S2 is by Aladdin aluminium oxide aqueous dispersions: isopropanol: water: ethanol amine is 1:3:3 by volume:
0.005 mixes.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, the electricity that is measured for it
Voltage curve is flowed, as shown in Figure 3；From the figure 3, it may be seen that the open-circuit voltage 0.86V of solar cell sample, short circuit current 4.4mA are filled out
Fill the factor 0.33, efficiency 1.24%.
Embodiment 4
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In CuInS described in step S12The preparation method of precursor solution is as follows: by 0.08mmol indium acetate, 0.4mmol thiocarbamide and
30 μ L propionic acid are dissolved in 0.4mL butylamine, and are carried out ultrasonic disperse and formed it into homogeneous solution, then again that 0.09mmol iodate is sub-
Copper is added in above-mentioned solution, and the ethylene glycol that overall solution volume 5% is added is uniformly mixed to get hole transmission layer presoma is arrived
Solution.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 5.2mA, fill factor 0.28, efficiency 1.23%.
Embodiment 5
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In CuInS described in step S12The preparation method of precursor solution is as follows: by 0.12mmol indium acetate, 0.6mmol thiocarbamide and
50 μ L propionic acid are dissolved in 0.8mL butylamine, and are carried out ultrasonic disperse and formed it into homogeneous solution, then again that 0.13mmol iodate is sub-
Copper is added in above-mentioned solution, and the ethylene glycol that overall solution volume 10% is added is uniformly mixed to get hole transmission layer presoma is arrived
Solution.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 5.0mA, fill factor 0.26, efficiency 1.1%.
Embodiment 6
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In the preparation method of the mixed solution of indium sulphur described in step S3 and perovskite are as follows: by the In (OAc) of 0.085mmol3、
The thiocarbamide of the CuI and 0.043mmol of 0.09mmol are dissolved into the perovskite solution that 1.6mL mass fraction is 40%.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 4.9mA, fill factor 0.26, efficiency 1.08%.
Embodiment 7
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In the preparation method of the mixed solution of indium sulphur described in step S3 and perovskite are as follows: by the In (OAc) of 0.34mmol3、
The thiocarbamide of the CuI and 0.17mmol of 0.36mmol are dissolved into the perovskite solution that 0.4mL mass fraction is 40%.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.86V, short circuit current 5.2mA, fill factor 0.25, efficiency 1.12%.
Embodiment 8
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In scraper height is respectively 30 μm, 45 μm, 60 μm, 90 μm in step S1-S4；Scraper speed be respectively 25mm/s, 25mm/s,
15mm/s、18mm/s。
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 5.0mA, fill factor 0.25, efficiency 1.06%.
Embodiment 9
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In annealing temperature is 90 DEG C in step S1-S4；Annealing time is respectively 15min, 10min, 10min, 15min.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 5.5mA, fill factor 0.25, efficiency 1.17%.
Embodiment 10
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In step S5 brushes one layer of carbon using the method for silk-screen printing in sample surfaces and starches, and makes its solidification at 100 DEG C.
Remaining is all the same with embodiment 1.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 4.8mA, fill factor 0.25, efficiency 1.02%.
Embodiment 11
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In specifically, first coating electronic transport layer on a flexible substrate is then successively coated with aluminium oxide on the basis of electron transfer layer
Layer, indium sulphur-perovskite composite layer, hole transmission layer, finally print carbon electrode.
S1, the solution that 20 μ electron transfer layers are scratched on flexible conducting substrate (2cm × 4cm) then anneal in 110 DEG C
10min, so that electron transfer layer be prepared on flexible conducting substrate；
Wherein, blade coating speed is 18mm/s, and scraper height is 30 μm；
The electron transfer layer precursor solution is [6.6]-phenyl-C61- methyl butyrate PCBM and/or [6.6]-phenyl-C71-
The chlorobenzene solution of methyl butyrate PCBM；The concentration of the electron transfer layer precursor solution is 10mg/ml；
S2,15 μ L alumina slurries are scratched on the electron transport layer, then in 100 DEG C of annealing 15min, thus in conductive substrates
Alumina layer is prepared；
Wherein, blade coating speed is 20mm/s, and scraper height is 50 μm；
The aluminium oxide is by Aladdin aluminium oxide aqueous dispersions: isopropanol: water: ethanol amine is 1:1.5:1.5 by volume:
0.001 mixes；
S3, the mixed solution that 15 μ L indium sulphurs and perovskite are scratched on alumina layer, then in 100 DEG C of annealing 15min, thus
Indium sulphur-perovskite composite layer is obtained on alumina layer；
Wherein, blade coating speed is speed 15mm/s, and scraper height is 70 μm；
The preparation method of the mixed solution of the indium sulphur and perovskite are as follows: by the In (OAc) of 0.17mmol3, 0.18mmol
The thiocarbamide of CuI and 0.085mmol is dissolved into (solvent N, N- dimethyl in the perovskite solution that 0.8mL mass fraction is 40%
Formamide)；
S4, the solution that 15 μ L hole transmission layers are scratched on indium sulphur-perovskite composite layer, then in 90 DEG C of annealing 10min, from
And hole transmission layer is obtained on indium sulphur-perovskite composite layer；
Wherein, blade coating speed is 25mm/s, and scraper height is 80 μm；
The hole transmission layer is CuInS2Layer, the CuInS2The preparation method of precursor solution is same as Example 1；
S5, one layer of carbon slurry is brushed using the method for silk-screen printing in sample surfaces, and makes its solidification at 110 DEG C.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 3.5mA, fill factor 0.38, efficiency 1.13%.
Comparative example 1
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In aluminium oxide described in step S2 is by aluminium oxide: isopropanol: water: ethanol amine be by volume 1:0.5:0.5:0.001 mixing and
At.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 3mA, fill factor 0.25, efficiency 0.64%.
Comparative example 2
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In CuInS described in step S12Ethylene glycol is not added in the configuration process of precursor solution.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.85V, short circuit current 3.5mA, fill factor 0.25, efficiency 0.74%.
Comparative example 3
Coating preparation method is scraped the present embodiment provides a kind of perovskite solar battery, compared with Example 1, difference exists
In scratching the perovskite solution that mass fraction is 40% in step S3, do not add indium sulphur in perovskite.
Gained solar battery is by measurement, in AM1.5,100mW/cm2Under the irradiation of etalon optical power, solar cell sample
Open-circuit voltage 0.75V, short circuit current 4mA, fill factor 0.25, efficiency 0.75%.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (10)
1. a kind of perovskite solar battery scrapes coating preparation method, which is characterized in that the described method comprises the following steps: using
Knife coating prepares hole transmission layer, alumina layer, indium sulphur-perovskite composite layer, electron transfer layer in conductive substrates,
In, the perovskite is CH3NH3PbI3；The aluminium oxide is by aluminium oxide: isopropanol: water: ethanol amine is 1:1-3 by volume:
1-3:0.001-0.005 mixing.
2. a kind of perovskite solar battery according to claim 1 scrapes coating preparation method, which is characterized in that the oxygen
Change the aqueous dispersions that aluminium is nano aluminium oxide, the solid content of aluminium oxide is 20%~25%, and the partial size of nano alumina particles is
5nm~10nm.
3. method according to claim 1 or 2, which is characterized in that the described method comprises the following steps:
S1, in conductive substrates scratch hole transmission layer precursor solution, then in 90 DEG C~100 DEG C annealing 10min~
15min, so that hole transmission layer be prepared in conductive substrates；Wherein, blade coating speed is 20mm/s~25mm/s, scrapes knife up
Degree is 20 μm~50 μm；
S2, alumina slurry is scratched on the hole transport layer, then in 90 DEG C~100 DEG C annealing 10min~15min, thus
Alumina layer is prepared in conductive substrates；Wherein, blade coating speed is 20mm/s~25mm/s, and scraper height is 35 μm~60 μ
m；
S3, on alumina layer scratch indium sulphur and perovskite mixed solution, then in 90 DEG C~100 DEG C annealing 10min~
20min, to obtain indium sulphur-perovskite composite layer on alumina layer；Wherein, blade coating speed be speed 15mm/s~
20mm/s, scraper height are 50 μm~80 μm；
S4, the solution that electron transfer layer is scratched on indium sulphur-perovskite composite layer, then in 90 DEG C~110 DEG C annealing 5min
~15min, to obtain electron transfer layer on indium sulphur-perovskite composite layer；Wherein, blade coating speed be 18mm/s~
25mm/s, scraper height are 60 μm~90 μm.
4. according to the method described in claim 3, it is characterized in that, the hole transmission layer is CuInS2Layer, the CuInS2Before
The preparation method for driving liquid solution is as follows: under nitrogen protection, by the indium acetate of every 0.08~0.12mmol, 0.4~0.6mmol
The propionic acid of thiocarbamide and 30~50 μ are dissolved into the butylamine of 0.4~0.8mL, and carry out ultrasonic disperse, formation homogeneous solution, then plus
The CuI for entering 0.09~0.13mmol, obtains CuInS2Precursor solution.
5. according to the method described in claim 4, it is characterized in that, the CuInS2Precursor solution further includes ethylene glycol, described
The additive amount of ethylene glycol is CuInS2The 5 ~ 10% of precursor solution total volume.
6. according to the method described in claim 5, it is characterized in that, the preparation side of the mixed solution of the indium sulphur and perovskite
Method are as follows: by the In (OAc) of every 0.085~0.34mmol3, the CuI of 0.09~0.36mmol, 0.043~0.17mmol thiocarbamide
It is dissolved into the n,N-Dimethylformamide solution of the perovskite of 0.4~1.6mL, the n,N-Dimethylformamide of the perovskite
The mass percent of perovskite is 20~40% in solution.
7. according to the method described in claim 6, it is characterized in that, the electron transfer layer precursor solution is [6.6]-benzene
The chlorobenzene solution of base-C61- methyl butyrate PCBM and/or [6.6]-phenyl-C71- methyl butyrate PCBM；The electron transfer layer
The concentration of precursor solution is 15mg/ml~20mg/ml.
8. being obtained the method according to the description of claim 7 is characterized in that further including preparing back electrode on the electron transport layer
Perovskite solar battery.
9. according to the method described in claim 8, it is characterized in that, the back electrode is any in metal electrode or carbon electrode
One or two kinds of combinations.
10. according to the method described in claim 9, it is characterized in that, the size of the conductive substrates be (2cm~10cm) ×
(2cm~10cm)；The conductive substrates are the transparent polymeric film with indium tin oxide ITO.
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