CN107946464B - A kind of perovskite solar battery and preparation method thereof based on barium titanate interface-modifying layer - Google Patents
A kind of perovskite solar battery and preparation method thereof based on barium titanate interface-modifying layer Download PDFInfo
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Abstract
The present invention relates to one kind to be based on BaTiO3The perovskite solar battery of interface-modifying layer, the perovskite solar battery include the FTO electro-conductive glass set gradually from bottom to top, compacted zone, electron transfer layer, interface-modifying layer, perovskite active layer and hole transmission layer.BaTiO is based on the invention also discloses above-mentioned3The preparation method of the perovskite solar battery of interface-modifying layer.Perovskite solar battery of the present invention uses BaTiO3Interface-modifying layer of the film as electron transfer layer and perovskite active layer is applied to perovskite solar cell, reduces the compound of interface light induced electron and hole, improves the photoelectric conversion efficiency of perovskite solar battery.
Description
Technical field
The invention belongs to battery preparation technology fields, and in particular to one kind is based on barium titanate (BaTiO3) interface-modifying layer
Perovskite solar battery and preparation method thereof.
Background technique
Perovskite solar battery is due to having many advantages, such as that absorption coefficient is big, absorption region is wide, and high conversion efficiency is in the sun
Energy field of batteries is paid close attention to by people extensively.Currently, the peak efficiency of perovskite solar battery has reached 22.1%
(Science, 2017,356:1376-1379).Studies have shown that the interfacial property of electron transfer layer and perovskite active layer is
A key factor for hindering perovskite solar battery efficiency to improve, because the defect state at interface will increase light induced electron and sky
Cave it is compound.In order to reduce the compound of interface photogenerated charge, a kind of effective method is exactly to be passed using some materials to electronics
Defeated layer is modified, and the defect state of interface is reduced, to reduce the compound of photogenerated charge, further increases the conversion effect of battery
Rate (Adv. Mater., 2016,28:3966;J. Am. Chem. Soc., 2016, 138:14998;J. Mater.
Chem. A, 2015,3:9160).Therefore, in order to further increase the transfer efficiency of perovskite solar battery, the task of top priority
It is to find a kind of excellent electron transfer layer decorative material, and be applied to perovskite solar cell.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of based on BaTiO3The perovskite of interface-modifying layer is too
Positive energy battery, uses BaTiO3Interface-modifying layer of the film as electron transfer layer and perovskite active layer is applied to calcium titanium
Mine solar cell reduces the compound of interface light induced electron and hole, improves the photoelectric conversion effect of perovskite solar battery
Rate.
BaTiO is based on the present invention also provides above-mentioned3The preparation method of the perovskite solar battery of interface-modifying layer.
To achieve the above object, the present invention adopts the following technical scheme:
One kind being based on BaTiO3The perovskite solar battery of interface-modifying layer, the perovskite solar battery include under
FTO electro-conductive glass, compacted zone, electron transfer layer, interface-modifying layer, perovskite active layer and the hole transport set gradually on and
Layer.
Specifically, the interface-modifying layer is obtained through following processing: interface-modifying layer precursor solution is spin-coated on electronics
In transport layer, anneal 40 ~ 70 min under the conditions of 450 ~ 550 DEG C；The interface-modifying layer precursor solution is that quality is dense
Ba (the NO of degree 0.3 ~ 2.4%3)2Aqueous solution.
It is a kind of above-mentioned based on BaTiO3The preparation method of the perovskite solar battery of interface-modifying layer comprising following step
It is rapid:
1) compacted zone precursor solution is spin-coated on clean, dry FTO electro-conductive glass, under the conditions of 450 ~ 500 DEG C
Anneal 30 ~ 50min, obtains compacted zone；
2) by electron transfer layer slurry for rotary coating on compacted zone, anneal 30 ~ 50min under the conditions of 450 ~ 500 DEG C, obtains electricity
Sub- transport layer；
3) on the electron transport layer by the spin coating of interface-modifying layer precursor solution, the annealing 40 ~ 70 under the conditions of 450 ~ 550 DEG C
Min obtains interface-modifying layer；
4) perovskite active layer precursor solution is spin-coated on interface-modifying layer, and chlorobenzene is added dropwise before rotation terminates,
Then sample is obtained into perovskite active layer in 100 ± 10 DEG C of 60 ± 10 min of heating；
5) hole transmission layer precursor solution is spin-coated on perovskite active layer, then uses hot steaming method coated film deposition one
Layer gold electrode to obtain the final product.
Specifically, in step 1), the compacted zone precursor solution by 0.25 mL butyl titanate, 5 mL dehydrated alcohols,
1 mL concentrated nitric acid and 0.5 mL water, which are mixed, to be obtained.
Further, in step 2, the electron transfer layer slurry is commercialization TiO2Slurry with dehydrated alcohol in mass ratio
Resulting dilution after 1:6 dilution.
Preferably, in step 3), interface-modifying layer precursor solution is spin-coated on electricity with 3000 ~ 5000 revs/min of revolving speed
In sub- transport layer, 30 ~ 60s of spin coating.
Preferably, in step 4), the perovskite precursor solution is by iodine carbonamidine (FAI), lead iodide (PbI2), bromine first
Amine (MABr) and lead bromide (PbBr2) be added in the mixed solution of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)
It mixes and obtains (DMF:DMSO=4:1, volume ratio), wherein the molar concentration difference of iodine carbonamidine, lead iodide, bromine methylamine and lead bromide
It is 1 M, 1.1 M, 0.2 M and 0.22M.
Preferably, in step 5), the hole transmission layer precursor solution is by 72.3 mg Spiro-OMeTAD, 28.8 μ
The acetonitrile solution dissolution for bis- (fluoroform sulphonyl) imine lithiums that l 4- tert .-butylpyridine and 17.5 μ l concentration are 520 mg/ml
It is obtained into 1ml chlorobenzene.
The present invention also provides using the above method be prepared based on BaTiO3The perovskite sun of interface-modifying layer
It can battery.
The present invention between electron transfer layer and perovskite active layer by being added one layer of BaTiO3Film is repaired as interface
Layer is adornd, to reduce the compound of photogenerated charge, improves the photoelectric conversion efficiency of perovskite solar battery, solves existing traditional calcium
Titanium ore solar battery electron transfer layer and the easily compound problem of perovskite active layer interface photogenerated charge.With prior art phase
Than, the invention has the following advantages that
1) present invention is used precursor B a (NO3)2Aqueous solution spin coating prepares BaTiO on the electron transport layer3Modifying interface
Layer.The advantages of this method: first is that can be by adjusting the pattern of the accurate control interface decorative layer of concentration, the thickness of precursor solution
The parameters such as degree optimize photoelectric conversion efficiency of the solar battery, obtain the corresponding best precursor solution concentration of highest transfer efficiency；Two
It is that the preparation method is easy to operate, is easy to grasp, is suitably applied the preparation of solar energy in large area battery；
2) prepared by the present invention to be based on BaTiO3Interface-modifying layer can effectively reduce electron transfer layer and perovskite active layer
The light induced electron of interface and hole it is compound, improve the short circuit current, open-circuit voltage and fill factor of solar cell.The present invention
Preparation based on BaTiO3The perovskite solar cell of interface-modifying layer compared with the perovskite solar cell of no interface-modifying layer,
Battery conversion efficiency effectively improves, and peak efficiency reaches 17.9%.
Detailed description of the invention
Fig. 1 is the TiO of no interface-modifying layer2With the TiO for having interface-modifying layer2/BaTiO3X-ray diffractogram (XRD).
The BaTiO marked in the figure for being located at 31.5 ° of diffraction maximums and belonging to cubic structure3；
Fig. 2 is no interface-modifying layer TiO2And have interface-modifying layer TiO2/BaTiO3UV-visible absorption spectrum；With
Without interface-modifying layer TiO2It compares, there is interface-modifying layer TiO2/BaTiO3The slightly red shift of absorption band edge, illustrate its band gap reduce；
(a) and (b) is no interface-modifying layer TiO respectively in Fig. 32And have interface-modifying layer TiO2/BaTiO3Scanning electron microscope
Scheme (SEM)；The granular size of modification front and back film, pattern do not have significant change, illustrate BaTiO3It is very thin to modify layer film, does not have
Influence TiO2Pattern；
Fig. 4 is based on no interface-modifying layer TiO2And have interface-modifying layer TiO2/BaTiO3The solar-electricity of (0.9 wt%)
Current-voltage (I-V) curve graph in pond.With based on no interface-modifying layer TiO2Battery compare, based on there is interface-modifying layer
TiO2/BaTiO3Solar cell photoelectric performance effectively improve.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
One kind being based on BaTiO3The perovskite solar battery of interface-modifying layer, the perovskite solar battery include under
FTO electro-conductive glass, compacted zone, electron transfer layer, interface-modifying layer, perovskite active layer and the hole transport set gradually on and
Layer.
It is above-mentioned to be based on BaTiO3The preparation method of the perovskite solar battery of interface-modifying layer, specifically includes following step
It is rapid:
1) preparation of compacted zone: the FTO electro-conductive glass of etching is sequentially placed into acetone, isopropanol and ethyl alcohol, each ultrasound
Cleaning 20 minutes is finally irradiated 20 minutes with UV.Compacted zone precursor solution is spin-coated on 3500 revs/min of revolving speed clean
Only, on dry FTO electro-conductive glass, anneal 40 min under the conditions of 500 DEG C, obtains compacted zone；The compacted zone presoma is molten
Liquid is mixed by 0.25 mL butyl titanate, 5 mL dehydrated alcohols, 1 mL concentrated nitric acid and 0.5 mL water and is obtained；
2) preparation of electron transfer layer: electron transfer layer slurry is spin-coated on compacted zone with 4000 revs/min of revolving speed,
Anneal 40 min under the conditions of 450 DEG C, obtains electron transfer layer；The electron transfer layer slurry is commercialization TiO2Slurry
Resulting dilution after (Dyesol, 30NR-D) is diluted with dehydrated alcohol 1:6 in mass ratio；
3) interface-modifying layer precursor solution the preparation of interface-modifying layer: is spin-coated on electricity with 5000 revs/min of revolving speed
In sub- transport layer (spin coating 30s), anneal 60min under the conditions of 500 DEG C, obtains interface-modifying layer；The interface-modifying layer forerunner
Liquid solution is the Ba (NO of mass concentration 0.3%3)2Aqueous solution；
4) preparation of perovskite active layer: by perovskite active layer precursor solution in 1000 rpm 10s and 6000 rpm
It is spin-coated on interface-modifying layer under conditions of 20s, and 100 μ l chlorobenzenes are added dropwise in 10s before rotation terminates, then by sample in 100
60 min are heated in DEG C heating dish, obtain perovskite active layer；The perovskite precursor solution is by iodine carbonamidine (FAI), iodine
Change lead (PbI2), bromine methylamine (MABr) and lead bromide (PbBr2) it is added to dimethylformamide (DMF) and dimethyl sulfoxide
(DMSO) it is mixed in mixed solution and obtains (DMF:DMSO=4:1, volume ratio), wherein iodine carbonamidine, lead iodide, bromine methylamine and bromine
The molar concentration for changing lead is 1 M, 1.1 M, 0.2 M and 0.22M respectively；
5) hole transmission layer precursor solution the preparation of hole transmission layer: is spin-coated on calcium with 4000 revs/min of speed
On titanium ore active layer, the gold electrode that hot steaming method coated film deposition a layer thickness is about 80nm is then used on the hole transport layer i.e.
.The hole transmission layer precursor solution is by 72.3 mg Spiro-OMeTAD, 28.8 μ l 4- tert .-butylpyridines and 17.5
μ l concentration is dissolved into 1ml chlorobenzene for the acetonitrile solution of bis- (fluoroform sulphonyl) imine lithiums of 520 mg/ml and obtains.
Embodiment 2 to 5
One kind being based on BaTiO3The perovskite solar battery of interface-modifying layer, the perovskite solar battery include under
FTO electro-conductive glass, compacted zone, electron transfer layer, interface-modifying layer, perovskite active layer and the hole transport set gradually on and
Layer.
It is above-mentioned to be based on BaTiO3The preparation method of the perovskite solar battery of interface-modifying layer is referring to embodiment 1, wherein
The difference is that the interface-modifying layer precursor solution is respectively mass concentration when preparing interface-modifying layer in step 3)
0.6%, 0.9%, 1.2%, 2.4% Ba (NO3)2Aqueous solution.
Reference examples
Perovskite solar battery difference from example 1 is that: be free of interface-modifying layer.
The photo electric of above-described embodiment preparation gained battery is tested using the solar cell test system of this field routine
Can, test result is shown in Table 1.
1 various concentration precursor solution of table prepares BaTiO3The photovoltaic performance of the resulting solar battery of interface-modifying layer is joined
Number
Table 1 is that based on no interface-modifying layer and have interface-modifying layer (to be prepared by the precursor solution of various concentration
BaTiO3Interface-modifying layer) perovskite solar battery photovoltaic performance parameter.As can be seen from Table 1: with no modifying interface
The solar battery of layer is compared, and BaTiO is based on3The photovoltaic performance parameter of modifying interface layer solar cell is all improved.
When interface-modifying layer precursor solution concentration is 0.9 wt%, cell photovoltaic performance is improved at most, photoelectric conversion efficiency (PCE)
It is increased to 17.9% by the 16.1% of no interface-modifying layer, short circuit current (Isc), open-circuit voltage (Voc) and fill factor (FF) is respectively
By 21.9 mA/cm of no interface-modifying layer2, 1.06 V and 69.3% be increased to 22.5 mA/cm2, 1.10 V and 71.7%.Experiment
The result shows that BaTiO3The introducing of interface-modifying layer effectively improves the transfer efficiency of perovskite solar cell.
Claims (6)
1. a kind of perovskite solar battery based on barium titanate interface-modifying layer, which is characterized in that the perovskite solar-electricity
Pond includes the FTO electro-conductive glass set gradually from bottom to top, compacted zone, electron transfer layer, interface-modifying layer, perovskite active layer
And hole transmission layer；
The interface-modifying layer is obtained through following processing: on the electron transport layer by the spin coating of interface-modifying layer precursor solution, In
Anneal 40 ~ 70 min under the conditions of 450 ~ 550 DEG C；The interface-modifying layer precursor solution is mass concentration 0.3 ~ 2.4%
Ba(NO3)2Aqueous solution；
By electron transfer layer slurry for rotary coating on compacted zone, anneal 30 ~ 50min under the conditions of 450 ~ 500 DEG C, obtains electron-transport
Layer；The electron transfer layer slurry is commercialization TiO2Resulting dilution after slurry is diluted with dehydrated alcohol 1:6 in mass ratio.
2. the preparation method of the perovskite solar battery described in claim 1 based on barium titanate interface-modifying layer, feature exist
In including the following steps:
1) compacted zone precursor solution is spin-coated on clean, dry FTO electro-conductive glass, is annealed under the conditions of 450 ~ 500 DEG C
30-50min obtain compacted zone；
2) by electron transfer layer slurry for rotary coating on compacted zone, anneal 30 ~ 50min under the conditions of 450 ~ 500 DEG C, obtains electronics and passes
Defeated layer；
3) on the electron transport layer by the spin coating of interface-modifying layer precursor solution, the annealing 40 ~ 70 under the conditions of 450 ~ 550 DEG C
Min obtains interface-modifying layer；
4) perovskite active layer precursor solution is spin-coated on interface-modifying layer, and chlorobenzene is added dropwise before rotation terminates, then
By sample in 100 ± 10 DEG C of 60 ± 10 min of heating, perovskite active layer is obtained；
5) hole transmission layer solution is spin-coated on perovskite active layer, is then using hot one layer of gold electrode of steaming method coated film deposition
；
In step 1), the compacted zone precursor solution is by 0.25 mL butyl titanate, 5 mL dehydrated alcohols, 1 mL concentrated nitric acid
It is mixed and obtains with 0.5 mL water；
In step 4), the perovskite precursor solution is to be added to dimethyl by iodine carbonamidine, lead iodide, bromine methylamine and lead bromide
It mixes and obtains in the mixed solution of formamide and dimethyl sulfoxide, wherein iodine carbonamidine, lead iodide, bromine methylamine and lead bromide rub
Your concentration is 1 M, 1.1 M, 0.2 M and 0.22M respectively.
3. the preparation method of the perovskite solar battery based on barium titanate interface-modifying layer as claimed in claim 2, feature
It is, in step 2, the electron transfer layer slurry is commercialization TiO2Gained after slurry is diluted with dehydrated alcohol 1:6 in mass ratio
Dilution.
4. the preparation method of the perovskite solar battery based on barium titanate interface-modifying layer as claimed in claim 2, feature
Be, in step 3), interface-modifying layer precursor solution with 3000 ~ 5000 revs/min of revolving speed spin coating on the electron transport layer,
30 ~ 60s of spin coating.
5. the preparation method of the perovskite solar battery based on barium titanate interface-modifying layer as claimed in claim 2, feature
It is, in step 5), the hole transmission layer precursor solution is by 72.3 mg Spiro-OMeTAD, 28.8 μ l 4- tert-butyls
The acetonitrile solution for bis- (fluoroform sulphonyl) imine lithiums that pyridine and 17.5 μ l concentration are 520 mg/ml is dissolved into 1ml chlorobenzene
Middle acquisition.
6. the perovskite sun based on barium titanate interface-modifying layer being prepared using any the method for claim 2 to 5
It can battery.
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| CN109103339A (en) * | 2018-08-16 | 2018-12-28 | 深圳市前海首尔科技有限公司 | A kind of preparation method of perovskite solar battery |
| CN109545972B (en) * | 2018-11-23 | 2022-12-02 | 浙江昱辉阳光能源江苏有限公司 | High-stability perovskite solar cell and preparation method |
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| CN110299454A (en) * | 2019-07-04 | 2019-10-01 | 湖南师范大学 | A kind of perovskite thin film solar battery and preparation method thereof using barium titanate as electron transport material |
| CN110676388B (en) * | 2019-10-14 | 2021-01-12 | 海南大学 | Perovskite solar cell modified based on 3,4,9, 10-perylene tetracarboxylic dianhydride and preparation method |
| CN110993803B (en) * | 2019-12-05 | 2023-03-21 | 常州大学 | Interface modification method of solar cell based on all-inorganic metal halide perovskite material |
| CN113113541B (en) * | 2021-04-08 | 2023-06-06 | 华侨大学 | Method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonylimide |
| CN114050189A (en) * | 2021-11-10 | 2022-02-15 | 苏州腾晖光伏技术有限公司 | Selenium antimony sulfide thin film solar cell with 3D structure and preparation method thereof |
| CN114369459B (en) * | 2022-01-10 | 2022-12-09 | 吉林大学 | Preparation method of lead-free rare earth perovskite quantum dot, product and application thereof |
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