CN110429182A - A kind of TiO2Combination electrode, the perovskite solar battery and preparation method thereof of AgNWs are embedded between bilayer film - Google Patents
A kind of TiO2Combination electrode, the perovskite solar battery and preparation method thereof of AgNWs are embedded between bilayer film Download PDFInfo
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Abstract
The present invention provides a kind of TiO2Combination electrode, the perovskite solar battery and preparation method thereof of AgNWs are embedded between bilayer film, the preparation process of combination electrode includes TiO2Fine and close electron transfer layer preparation, TiO2Upper surface deposits preparation and the TiO of the electrode of AgNWs2The preparation of the combination electrode of AgNWs is embedded between bilayer film；The present invention also protects the perovskite solar battery and preparation method thereof comprising above-mentioned combination electrode；The present invention effectively inhibits perovskite thin film and TiO2Between formed space limit charge, promote the separation of exciton and transport；Photoelectronic transmission speed in perovskite thin film is improved simultaneously, improves photoelectric conversion efficiency and fill factor, inhibits sluggish；And the quality of perovskite thin film is promoted, contact of the optimization perovskite thin film with lower layer hole transmission layer effectively improves the photoelectric conversion efficiency of device, realistic meaning with higher.
Description
Technical field
The present invention relates to luminescence display technical field, specially a kind of TiO2The compound electric of AgNWs is embedded between bilayer film
Pole, perovskite solar battery and preparation method thereof.
Background technique
The energy is the basis that human society is depended on for existence and development, with increasingly developed, need of the people to the energy of society
The amount of asking also shows the trend of explosive growth, and the problems such as bring energy shortages, ecological environmental pollution also becomes increasingly conspicuous therewith.Mesh
Prehuman research and develop relatively broad new energy specifically include that solar energy, water energy, nuclear energy, wind energy, Hydrogen Energy, biomass energy with
And geothermal energy etc..Wherein using solar energy as the clean energy resource of representative, have the advantages that in other energy forms incomparable.The sun
Energy storage capacity is abundant, transportation problem is also not present, the annual earth, which receives the energy from the sun, makes the three of whole world wastage in bulk or weight
Wan Bei, therefore storage can be carried out in situ and utilized, while waste water, exhaust gas, waste material etc. will not be discharged in solar energy use process.
For the mode of solar energy conversion mainly by photochemistry, photo-thermal and three kinds of photoelectric conversion, solar battery is exactly benefit
The technology of photoelectric conversion is carried out with the photovoltaic effect of semiconductor devices, that is, is referred to by receiving incident sunlight, directly
It converts the luminous energy of absorption to the optical device of electromotive force, is substantially exactly the p-n junction of a large area, its working principle is that sharp
With the photovoltaic effect of the p-n junction of semiconductor.Solar battery according to the type of material can be divided into silica-based solar cell,
The quick magnificent solar battery of inorganic compound thin film solar battery, organic polymer thin film solar battery, dyestuff and perovskite
Solar battery.
Perovskite solar battery is a kind of new and effective thin-film solar cells risen in recent years, typical perovskite
Solar battery structure is successively from top to bottom: transparent conducting glass (light anode), n-type semiconductor (electron transfer layer),
Perovskite-type material (light absorbing layer), p-type semiconductor material (hole transmission layer), to electrode (photocathode), it is mainly to have
Machine-inorganic hybridization lead halogen perovskite CH3NH3PbX3As the solar cell device of light absorbing layer preparation, photoelectric properties
Promotion it is very rapid；At the beginning of 2015, Korea Research Inst. of Chemical Technology (KRICT) has authenticated photoelectric conversion efficiency by NREL and reaches
To 22.1% perovskite solar battery, very wide application prospect is shown.
But since the transmission of the per area per time electrons and holes of the perovskite solar battery of traditional structure is flat
Weighing apparatus is difficult to effectively adjust, and often will cause perovskite cell photoelectric decrease in efficiency.
AgNWs film has good optical transmittance and high conductivity, and therefore, it may be used as manufacture flat-panel monitor
With the transparent electrode of solar battery.The adjustment carried out on AgNWs can make the transfer of hole and electronics more balanced.Mesh
Before, it include TiO2Perovskite solar battery with AgNWs includes only TiO2Battery and AgNWs without AgNWs are in TiO2Layer
On battery；Only TiO2Battery without AgNWs, structure ITO/TiO2/MAPbIxCl3- x/Spiro-OMeTAD/Ag's
Device surface charge is more, and photoelectric conversion efficiency need to be improved；AgNWs is in TiO2Battery on layer, structure: ITO/TiO2-
AgNWs is (in TiO2On surface)/MAPbIxCl3- x/Spiro-OMeTAD/Ag, the AgNWs in such structure be easy and
MAPbIxCl3- x forms Ag-AgI and forms complex centre, declines the photoelectric conversion efficiency of battery.
Summary of the invention
The purpose of the present invention is to solve the deficiencies of above-mentioned technology, provide a kind of TiO2AgNWs is embedded between bilayer film
Preparation method, perovskite solar battery and the preparation method of combination electrode, TiO2AgNWs is embedded between bilayer film to be able to suppress
Perovskite thin film and TiO2Between formed space limit charge, promote the separation of exciton and transport；Perovskite thin film is improved simultaneously
In photoelectronic transmission speed, improve photoelectric conversion efficiency and fill factor, inhibit sluggish；Also make combination electrode and calcium titanium ore bed
It efficiently separates, forms compacted zone, the influence for protecting them from the iodine of perovskite forms complex centre；And promote calcium
The quality of titanium ore film, contact of the optimization perovskite thin film with lower layer hole transmission layer, effectively improves the photoelectric conversion of device
Efficiency.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of TiO2The preparation method of the combination electrode of AgNWs is embedded between bilayer film, comprising the following steps:
S1、TiO2Fine and close electron transfer layer preparation: the TiO that will be prepared2In sol-gel deposition to substrate, after dry
Deposition makes surfacing again, and obtains TiO in 350~400 DEG C of 30~40min of annealing in air atmosphere2Fine and close electronics passes
Defeated layer；
S2、TiO2The preparation of the electrode of upper surface deposition AgNWs: AgNWs is dispersed in ethylene glycol and obtains mass concentration
For the AgNWs dispersion liquid of 5mg/mL, AgNWs dispersion liquid is then deposited on the TiO that S1 is obtained2On fine and close electron transfer layer, and
In 180~200 DEG C of 20~30min of annealing in air atmosphere, TiO is obtained2The electrode of upper surface deposition AgNWs；
S3、TiO2The combination electrode preparation of AgNWs: the TiO that will be prepared is embedded between bilayer film2It is nanocrystalline to deposit to
The TiO that S2 is obtained2Upper surface deposits on the electrode of AgNWs, and in 100~300 DEG C of 10~120min of annealing in air atmosphere,
Obtain TiO2The combination electrode of AgNWs is embedded between bilayer film.
Preferably, the substance withdrawl syndrome of TiO2 collosol and gel is 0.2mol/L in S1；
The specific preparation process of the TiO2 collosol and gel are as follows: by butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol according to 2.39:
The volume ratio of 1.06:17 is uniformly mixed and obtains solution A, by hydrochloric acid, deionized water and ethyl alcohol according to the volume of 0.08:0.85:17
Solution B is obtained than being uniformly mixed, solution B is added in solution A, stirs 30~40min, placement is aged for 24 hours, is obtained
TiO2 collosol and gel.
Preferably, drying temperature is 100 DEG C in the S1, and drying time is 10~20min.
Preferably, TiO in the S32Nanocrystalline mass concentration is 150g/L；
The TiO2Nanocrystalline preparation process are as follows: mix butyl titanate and isopropanol according to the volume ratio of 3.7:1
Uniformly, and in ice bath 30~35min is stirred, the glacial acetic acid aqueous solution that volume fraction is 20~25% is added and is uniformly mixed,
By mixed liquor in 220 DEG C of hydro-thermal reaction 12h, polyethylene glycol is added after the reaction was completed and is cleaned by ultrasonic concentration, obtains mass concentration
For 150g/L TiO2It is nanocrystalline.
The TiO that the present invention also protects above-mentioned preparation method to be prepared2The combination electrode of AgNWs is embedded between bilayer film.
The present invention is also protected comprising above-mentioned TiO2The perovskite solar-electricity of the combination electrode of AgNWs is embedded between bilayer film
The preparation method in pond, comprising the following steps:
(1) TiO is prepared2AgNWs combination electrode is embedded between bilayer film；
(2) under inert gas shielding, by CH3NH3I and PbCl2It is uniformly mixed according to the molar ratio of 3:1 with DMF, and in
60 DEG C stir to get the perovskite precursor solution that mass fraction is 30%；
(3) the perovskite precursor solution that step (2) obtains is deposited on the TiO that step (1) obtains2It is embedding between bilayer film
Enter the combination electrode of AgNWs, and carry out stage annealing under air atmosphere, obtains MAPbIxCl3-xLight absorbing layer；
(4) MAPbI for obtaining Spiro-OMeTAD liquid deposition to step (3)xCl3-xHole is obtained on light absorbing layer
Transport layer；
(5) Ag electrode is deposited on the hole transmission layer of step (4), obtains perovskite solar battery.
Preferably, in step (4) Spiro-OMeTAD solution process for preparation are as follows: Spiro-OMeTAD powder is pressed with chlorobenzene
It is uniformly mixed, sequentially adds the acetonitrile solution of lithium salts and Tributyl phosphate ester and is mixed according to the solid-liquid ratio of 72.3mg:1mL
1~1.5h obtains the solution of Spiro-OMeTAD；
Wherein the acetonitrile solution concentration of lithium salts is 520mg/mL, the acetonitrile solution of lithium salts, Tributyl phosphate ester and chlorobenzene
Volume ratio is 10.9:8.8:500.
Preferably, in step (3) stage annealing process are as follows: anneal 30min at prior to 80 DEG C, then at 100 DEG C
Anneal 60min.
Preferably, TiO in step (1)2The substrate being embedded in the combination electrode of AgNWs between bilayer film is ito glass base
Plate, the preprocessing process of substrate are as follows: cleaned respectively using boiling water, deionized water and dehydrated alcohol, the stirring in step (2)
Time is 10~12h.
The present invention also protects the perovskite solar battery being prepared using above-mentioned preparation method, which includes under
The TiO set gradually on and2Composite electrode layers, the MAPbI of AgNWs are embedded between bilayer filmxCl3-xLight absorbing layer, Spiro-
OMeTAD hole transmission layer and Ag electrode layer, the TiO2Between bilayer film be embedded in AgNWs composite electrode layers with a thickness of 50
~200nm, the MAPbIxCl3-xLight absorbing layer with a thickness of 200~400nm, the Spiro-OMeTAD hole transmission layer
With a thickness of 10~150nm, the Ag electrode layer with a thickness of 100nm.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the present invention passes through TiO2The setting of AgNWs combination electrode, effectively inhibition perovskite thin film are embedded between bilayer film
Space is formed between TiO2 and limits charge, is promoted the separation of exciton and is transported；
2, the present invention improves photoelectronic transmission speed in perovskite thin film, improves photoelectric conversion efficiency and fill factor,
Inhibit sluggish.
3, invention passes through TiO2It is embedded in the setting of AgNWs combination electrode between bilayer film, improves roughness and TiO2 and calcium
Interface between titanium ore reduces the series resistance of perovskite solar battery.
4, AgNWs is embedded in TiO2 by the present invention, they are efficiently separated with calcium titanium ore bed, is formed compacted zone, is protected it
Form complex centre from the influence of the iodine of perovskite.
5, the present invention promotes the quality of perovskite thin film, contact of the optimization perovskite thin film with lower layer hole transmission layer.
Detailed description of the invention
Fig. 1 be embodiment 1 and the combination electrode in comparative example 1 scanning figure and combination electrode on deposit
MAPbIxCl3-xThe scanning figure of light absorbing layer film；In Fig. 1: (a) being TiO2The front elevation of-AgNWs (insertion) electrode；(b) it is
TiO2The front elevation of-AgNWs (upper surface) electrode；It (c) is TiO2The MAPbI deposited on-AgNWs (insertion) electrodexCl3-xLight is inhaled
Receive the scanning figure of layer film；It (d) is TiO2The MAPbI deposited on-AgNWs (upper surface) electrodexCl3-xLight absorbing layer film is swept
Tracing；
Fig. 2 is the electrochemical impedance of different perovskite solar batteries prepared by embodiment 1, comparative example 1 and comparative example 2
Spectrum；In Fig. 2: being (a) electrochemical impedance spectroscopy tested under open-circuit voltage, be (b) leakage current of solar battery in the case of dark-state
Relation curve；
Fig. 3 is embodiment 1TiO2The MAPbI deposited on-AgNWs (embedded) combination electrodexCl3-xLight absorbing layer film
XRD diagram；
Fig. 4 is the J-V curve of different perovskite solar batteries prepared by embodiment 1, comparative example 1 and comparative example 2；
Fig. 5 is the PCE histogram of 30 devices in the perovskite solar battery of embodiment 1 on electron transfer layer (ETL)
Figure.
Specific embodiment
Below by specific embodiment example, the present invention will be described in detail.The scope of the present invention is not limited to the tool
Body embodiment.
The preparation of AgNWs is referring to following documents in the present invention: 1, Yang Z, Wang M, Song X, et
al.Engineering the plasmonic optical properties of cubic silver
nanostructures based on Fano resonance[J].JOURNAL OF CHEMICAL PHYSICS,2013,
139(16):3669.2、Yang Z,Wang M,Song X,et al.High-performance ZnO/Ag Nanowire/
ZnO composite film UV photodetectors with large area and low operating
voltage[J].Journal of Materials Chemistry C,2014,2(21):4312-4319.3、Yang Z,
Wang M,Yan G,et al.An Improved Method to Synthesize Silver Nanorods and Study
on Their Optical Properties e[J].Chemistry Letters,2013,42(9):1016-1017。
Embodiment 1
The present embodiment provides include TiO2The perovskite solar battery system of the combination electrode of AgNWs is embedded between bilayer film
Preparation Method, comprising the following steps:
(1) TiO is prepared2The combination electrode of AgNWs is embedded between bilayer film；
S1、TiO2The preparation of fine and close electron transfer layer: by the mixed of 2.3856mL butyl titanate and 1.057mL acetylacetone,2,4-pentanedione
The dehydrated alcohol that solution is dissolved in 17mL is closed, is uniformly mixed and obtains solution A；By the deionization of the hydrochloric acid of 0.08125mL and 0.85mL
Water is uniformly mixed to obtain B solution with the dehydrated alcohol of 17mL；B solution is slowly added to stir 30min after solution A, then is placed for 24 hours
It is aged, obtains TiO2Collosol and gel；The TiO that will be prepared2Collosol and gel is spun to successively by boiling water, deionized water
With washes of absolute alcohol on dry ito glass substrate, spin coating process revolving speed is 3000rpm, spin-coating time 20s, by spin coating
Good substrate is placed in constant temperature blast drying oven, and spin coating makes surfacing again after 100 DEG C of annealing 10min, drying, that is, is filled out
The hole being likely to occur is filled, finally ensures TiO in 400 DEG C of annealing 30min in air atmosphere in Muffle furnace2Electron-transport
Layer it is complete, obtain TiO2Fine and close electron transfer layer；
S2、TiO2The preparation of the electrode of upper surface deposition AgNWs: AgNWs is dispersed in ethylene glycol and obtains mass concentration
For the AgNWs dispersion liquid of 5mg/mL, AgNWs dispersion liquid is then spin-coated on the TiO that S1 is obtained2On fine and close electron transfer layer, rotation
Painting process revolving speed is 1000rpm, spin-coating time 20s, and obtains TiO in 200 DEG C of annealing 20min in air atmosphere2Upper table
The electrode of face deposition AgNWs；
S3、TiO2The preparation of the combination electrode of AgNWs is embedded between bilayer film: by 37mL butyl titanate and 10mL isopropyl
Alcohol is uniformly mixed, and 30min is stirred in ice bath, and 80mL glacial acetic acid and 250mL deionized water are mixed to get glacial acetic acid solution,
The mixed solution of butyl titanate and isopropanol is uniformly mixed with glacial acetic acid aqueous solution, by mixed liquor in 220 in water heating kettle
The polyethylene glycol of 4g is added after the reaction was completed and is cleaned by ultrasonic concentration by DEG C hydro-thermal reaction 12h, obtains mass concentration as 150g/L's
TiO2It is nanocrystalline；The TiO that will be prepared2The nanocrystalline TiO for being spun to S2 and obtaining2Upper surface deposits on the electrode of AgNWs, and
In 300 DEG C of annealing 30min in air atmosphere in Muffle furnace, can either remaining solvent in thin evaporated film, and can enhance
TiO2Nanocrystalline crystallinity, obtains with a thickness of 50TiO2The combination electrode of AgNWs is embedded between bilayer film；
(2) by TiO2The combination electrode that AgNWs is embedded between bilayer film is transferred in the glove box full of nitrogen, will
CH3NH3I and PbCl2It is uniformly mixed according to the molar ratio of 3:1 with DMF, and stirring 10h to obtain mass fraction in 60 DEG C is 30%
Perovskite precursor solution；
(3) the perovskite precursor solution that step (2) obtains is spin-coated on the TiO that step (1) obtains2It is embedding between bilayer film
Enter on the combination electrode of AgNWs, the revolving speed of spin coating process is 4000rpm, spin-coating time 40s, and in air in Muffle furnace
Stage annealing is carried out under atmosphere, that is, prior to 80 DEG C at anneal 30min, then in 100 DEG C of annealing 60min, obtain thickness
Degree is the MAPbI of 200nmxCl3-xLight absorbing layer；
(4) the Spiro-OMeTAD powder of 72.3mg is uniformly mixed with 1mL chlorobenzene, sequentially adding 21.8 μ L concentration is
The acetonitrile solution of the lithium salts of 520mg/mL and 17.6 μ L Tributyl phosphate esters and be mixed 1h obtain Spiro-OMeTAD point
Dispersion liquid；The MAPbI that Spiro-OMeTAD liquid deposition to step (3) is obtainedxCl3-xOn light absorbing layer, the revolving speed of spin coating process
For 2000rpm, spin-coating time 30s, the Spiro-OMeTAD hole transmission layer with a thickness of 150nm is obtained；
(5) the Ag electrode that deposition thickness is 100nm on the Spiro-OMeTAD hole transmission layer of step (4), obtains calcium
Titanium ore solar battery.
Embodiment 2
It is identical as the structure of embodiment 1, the difference is that MAPbIxCl3-xLight absorbing layer with a thickness of 400nm.
Embodiment 3
It is identical as the structure of embodiment 1, unlike AgNWs composite electrode layers with a thickness of 200nm.
Embodiment 4
It is identical as the structure of embodiment 1, unlike Spiro-OMeTAD hole transmission layer with a thickness of 10nm.
Comparative example 1
It is identical as the process of embodiment 1, the difference is that the electrode in step (1) is TiO2The electricity of upper surface deposition AgNWs
Pole, the i.e. structure of perovskite battery are as follows: ITO/TiO2-AgNws(TiO2Upper surface)/MAPbIxCl3-x/Spiro-OMeTAD/
Ag。
Comparative example 2
It is identical as the process of embodiment 1, unlike in step (1) directly on substrate depositing Ti O2, i.e., perovskite electricity
The structure in pond are as follows: ITO/TiO2/MAPbIxCl3-x/Spiro-OMeTAD/Ag。
We are to the combination electrode and correspondence in the perovskite solar battery of embodiment 1, comparative example 1 and comparative example 2
Battery carried out performance test and morphology characterization；The combination electrode of embodiment 1 is named as TiO by us2- AgNWs (insertion
Formula) electrode, the electrode in comparative example 1 is named as TiO2- AgNws (upper surface) electrode.
Fig. 1 be embodiment 1 and the combination electrode in comparative example 1 scanning figure and combination electrode on deposit
MAPbIxCl3-xThe scanning figure of light absorbing layer film；Wherein (a) is TiO2The front elevation of-AgNWs (embedded) electrode；(b) it is
TiO2The front elevation of-AgNWs (upper surface) electrode；It (c) is TiO2The MAPbI deposited on-AgNWs (embedded) electrodexCl3-xLight
Absorb the scanning figure of layer film；It (d) is TiO2The MAPbI deposited on-AgNWs (upper surface) electrodexCl3-xLight absorbing layer film
Scanning figure；From Fig. 1 (c) as can be seen that TiO2The MAPbI deposited on-AgNWs (embedded) electrode3-xClxFilm illustrates phase
To smooth and uniform surface, this also illustrates the TiO of the spin coating on Ag nano wire2It is nanocrystalline to promote lower thin film
Film forming characteristics is plane MAPbI3-xClxThe film forming of several functional layers lays firm foundations below perovskite solar battery,
Because the film forming of film has very big relationship with substrate, smooth substrate is beneficial to film and is formed；It can see in Fig. 1 (d),
TiO2The MAPbI deposited on-AgNWs (upper surface) electrodexCl3-xThere are many folds on the surface of light absorbing layer film, is on the one hand
Due to MAPbI3-xClxFilm has directly been made on latticed AgNWs, and the out-of-flatness of substrate causes, and on the other hand may be
Due to MAPbI3-xClxHalide ion in film is reacted with AgNWs's, plays certain destruction to the formation of film.
Table 1 is the performance parameter of different perovskite solar batteries prepared by embodiment 1, comparative example 1 and comparative example 2
Table, as it can be seen from table 1 TiO2- AgNWs (embedded) electrode is able to ascend the transmission and separation of charge, promotes solar-electricity
The photoelectric conversion efficiency in pond.
The different perovskite solar cell properties parameter lists of table 1
Fig. 2 is the electrochemical impedance of different perovskite solar batteries prepared by embodiment 1, comparative example 1 and comparative example 2
Spectrum (b) is closed wherein (a) is the electrochemical impedance spectroscopy tested under open-circuit voltage for the leakage current of solar battery in the case of dark-state
It is curve；From Fig. 2 (a) and (b) as can be seen that TiO2The series resistance of-AgNWs (embedded) solar battery is compared to TiO2
Compacted zone has obtained apparent reduction, and TiO2The series resistance of-AgNWs (upper surface) solar battery is relative to TiO2-
The series resistance of AgNWs (embedded) solar battery slightly reduces, and illustrates in TiO2With MAPbIxCl3-xBetween perovskite material
AgNWs not play the role of drop low-resistance, the possible reason is silver halide is a kind of conduction because generate silver halide
The very poor material of property；Namely illustrate, in TiO2With MAPbIxCl3-xAgNWs between perovskite material causes under battery performance
The main reason for drop may be since complex centre is caused or MAPbIxCl3-xDamage between perovskite material causes photoelectricity
The reduction of subflow.
Fig. 3 is embodiment 1TiO2The MAPbI deposited on-AgNWs (embedded) combination electrodexCl3-xLight absorbing layer film
XRD diagram, from figure 3, it can be seen that TiO2The MAPbI deposited on-AgNWs (embedded) combination electrodexCl3-xOn light absorbing layer film
There is not the peak of AgI, illustrates the AgNWs and MAPbI of insertionxCl3-xLight absorbing layer film efficiently separates.
Fig. 4 is the J-V curve of different perovskite solar batteries prepared by embodiment 1, comparative example 1 and comparative example 2, figure
5 be the PCE histogram of 30 devices in the perovskite solar battery of embodiment 1 on electron transfer layer (ETL)；It can from Fig. 4
To find out, only TiO is embedded in the electrode and comparative example 2 of AgNWs in embodiment 12Device in there are higher carrier is close
Degree, this is because the AgNWs of insertion reduces work function and improves TiO2Fermi level, to enhance the built-in of device
Current potential；The adjusting of local charge density is crucial for the balance of electrons and holes flux.From fig. 5, it can be seen that embodiment 1
In in TiO2AgNWs is embedded in compacted zone can solve AgNWs in TiO2The problem of Ag-AgI is formed at the top of compacted zone, Ke Yiti
The stability of high device；Therefore, there is the device of insertion electrode to show good repeatability.
Table 2 is the photovoltaic parameter for scanning 1 perovskite solar battery of embodiment from different directions, from table 2 it can be seen that base
The solar cell device of Embedded A gNWs combination electrode can reduce the J-V lag in different scanning direction now in embodiment 1
As, and improve average PCE.
Table 2 scans the photovoltaic parameter of 1 perovskite solar battery of embodiment from different directions
By above-mentioned performance test it is found that being embedded in TiO in cavity transmission ability and embodiment 12AgNWs in film is more
Match, which eliminates the charge and TiO of limited space simultaneously2The surface potential of close layer increases.These results are led
V is causedocImprovement.According to the data of offer, the performance of the perovskite solar battery of embodiment 1 is better than comparative example 1 and comparison
The performance of the perovskite solar battery of example 2, with the perovskite solar battery of the embedded manufacture of AgNWs better than only TiO2Nothing
AgNWs and TiO2The performance of the solar battery of-AgNWs (upper surface).
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of TiO2The preparation method of the combination electrode of AgNWs is embedded between bilayer film, which comprises the following steps:
S1、TiO2The preparation of fine and close electron transfer layer: the TiO that will be prepared2In sol-gel deposition to substrate, after drying again
Secondary deposition makes surfacing, and obtains TiO in 350~400 DEG C of 30~40min of annealing in air atmosphere2Fine and close electron-transport
Layer；
S2、TiO2The preparation of the electrode of upper surface deposition AgNWs: it is 5mg/ that AgNWs, which is dispersed in ethylene glycol, and obtains mass concentration
The AgNWs dispersion liquid of mL, is then deposited on the TiO that S1 is obtained for AgNWs dispersion liquid2On fine and close electron transfer layer, and in air
In 180~200 DEG C of 20~30min of annealing in atmosphere, TiO is obtained2The electrode of upper surface deposition AgNWs；
S3、TiO2The preparation of the combination electrode of AgNWs: the TiO that will be prepared is embedded between bilayer film2It is nanocrystalline to deposit to S2
Obtained TiO2Upper surface deposits on the electrode of AgNWs, and obtains in air atmosphere in 100~300 DEG C of 10~120min of annealing
To TiO2The combination electrode of AgNWs is embedded between bilayer film.
2. a kind of TiO according to claim 12The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special
Sign is, TiO in the S12The substance withdrawl syndrome of collosol and gel is 0.2mol/L；
The TiO2The specific preparation process of collosol and gel are as follows: by butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol according to 2.39:1.06:
17 volume ratio is uniformly mixed and obtains solution A, and hydrochloric acid, deionized water and ethyl alcohol are mixed according to the volume ratio of 0.08:0.85:17
Solution B uniformly is obtained, solution B is added in solution A, stirs 30~40min, placement is aged for 24 hours, obtains TiO2Colloidal sol
Gel.
3. a kind of TiO according to claim 12The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special
Sign is that drying temperature is 100 DEG C in the S1, and drying time is 10~20min.
4. a kind of TiO according to claim 12The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special
Sign is, TiO in the S32Nanocrystalline mass concentration is 150g/L；
The TiO2Nanocrystalline preparation process are as follows: butyl titanate and isopropanol are uniformly mixed according to the volume ratio of 3.7:1,
And 30~35min is stirred in ice bath, it adds the glacial acetic acid aqueous solution that volume fraction is 20~25% and is uniformly mixed, will mix
Polyethylene glycol is added after the reaction was completed and is cleaned by ultrasonic concentration, obtaining mass concentration is 150g/ in 220 DEG C of hydro-thermal reaction 12h for liquid
The TiO of L2It is nanocrystalline.
5. the TiO that preparation method according to any one of claims 1 to 4 is prepared2It is embedded in AgNWs's between bilayer film
Combination electrode.
6. a kind of preparation method of perovskite solar battery, which is characterized in that include TiO in the perovskite solar battery2
The combination electrode of AgNWs is embedded between bilayer film, comprising the following steps:
(1) TiO is prepared2The combination electrode of AgNWs is embedded between bilayer film；
(2) under inert gas shielding, by CH3NH3I and PbCl2It is uniformly mixed according to the molar ratio of 3:1 with DMF, and in 60 DEG C
Stir to get the perovskite precursor solution that mass fraction is 30%；
(3) the perovskite precursor solution that step (2) obtains is deposited on the TiO that step (1) obtains2It is embedded between bilayer film
On the combination electrode of AgNWs, and stage annealing is carried out under air atmosphere, obtain MAPbIxCl3-xLight absorbing layer；
(4) MAPbI for obtaining Spiro-OMeTAD liquid deposition to step (3)xCl3-xHole transport is obtained on light absorbing layer
Layer；
(5) Ag electrode is deposited on the hole transmission layer of step (4), obtains perovskite solar battery.
7. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (4)
The process for preparation of Spiro-OMeTAD solution are as follows: mix Spiro-OMeTAD powder according to the solid-liquid ratio of 72.3mg:1mL with chlorobenzene
Uniformly, sequentially add lithium salts acetonitrile solution and Tributyl phosphate ester and be mixed 1~1.5h obtain Spiro-OMeTAD
Solution；
Wherein the acetonitrile solution concentration of lithium salts is 520mg/mL, the volume of the acetonitrile solution of lithium salts, Tributyl phosphate ester and chlorobenzene
Than for 10.9:8.8:500.
8. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (3)
The process of stage annealing are as follows: anneal 30min at prior to 80 DEG C, then in 100 DEG C of annealing 60min.
9. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (1)
TiO2The substrate being embedded in the combination electrode of AgNWs between bilayer film is ito glass substrate, the preprocessing process of substrate are as follows: point
It is not cleaned successively using boiling water, deionized water and dehydrated alcohol, the mixing time in step (2) is 10~12h.
10. the perovskite solar battery obtained according to any preparation method of claim 6~9, which is characterized in that packet
Include the TiO set gradually from bottom to top2Composite electrode layers, the MAPbI of AgNWs are embedded between bilayer filmxCl3-xLight absorbing layer,
Spiro-OMeTAD hole transmission layer and Ag electrode layer, the TiO2The thickness of the composite electrode layers of AgNWs is embedded between bilayer film
Degree is 50~200nm, the MAPbIxCl3-xLight absorbing layer with a thickness of 200~400nm, the hole Spiro-OMeTAD passes
Defeated layer with a thickness of 10~150nm, the Ag electrode layer with a thickness of 100nm.
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