CN109888111A - The perovskite solar battery and method of blade coating printing preparation entirely under a kind of air conditions - Google Patents
The perovskite solar battery and method of blade coating printing preparation entirely under a kind of air conditions Download PDFInfo
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Abstract
The invention belongs to technical field of solar batteries, disclose under a kind of air conditions the perovskite solar battery structure and method of blade coating printing preparation entirely, the glass baseplate coated with the tin oxide of detergent ultrasonic cleaning Fluorin doped, ionized water, acetone, isopropanol are successively washed, then the FTO substrate cleaned in advance is cleaned to the contact to improve PEDOT:PSS with substrate in UV- ozone cleaner；It by poly styrene sulfonate aqueous solution isopropanol and filters, then blade coating preparation film layer；By assisting heating means preparing perovskite thin film；Perovskite precursor solution PbAc2·3H2The molar ratio of O:MAI is 1:3, is filtered with filter, preheats, is applied on substrate I TO glass, obtains film.Technical support is provided the beneficial effects of the invention are as follows the improved efficiency for prepare with scale large area perovskite solar cell device.
Description
Technical field
The invention belongs to the calcium that entirely prepared by blade coating printing under technical field of solar batteries more particularly to a kind of air conditions
Titanium ore solar battery and method.
Background technique
Currently, the prior art commonly used in the trade is as follows:
Since the 21th century, " environmentally friendly ", " sustainable development " are always the hot issue of China's concern, because
Many environmental problems all crises caused by energy shortage and greenhouse effects are to our existence, and wherein main cause is to fire on a large scale
It burns and generates a large amount of carbon dioxide.For the increasingly depleted of fossil energy, the problems such as environmental problem is got worse, people have been opened
Beginning sets about creating renewable energy using some low-carbon emission generation technologies, such as passes through water generating, passes through wind-power electricity generation and light
Volt power generation etc. is received more and more attention and is studied.In these methods, due to most of sunlight that earth surface receives
In energy be not yet received and make full use of, therefore there is great potential, light using the energy that photovoltaic power generation technology applies sunlight
Volt generation technology can convert the solar into available electrical energy and utilize photoelectric effect.It has attracted the important research and development from countries in the world
Interest.
Solar battery is to absorb light by semiconductor material to excite and generate photoelectronic device, and can be used
External circuit stores and uses generated photoelectric current.Since 1954, the scientist Calvin of AT&T Labs, the U.S.
Fuller, Gerald Pearson and Daryl Chapin have invented the practical sun that first photoelectric conversion efficiency is only 6%
It can battery.Up to the present, it has evolved to the third generation.Solar battery technology achieves significant progress.In particular, silicon
Solar battery commercially produces the daily household electric for enabling solar battery to travel to people from initial deep space satellite
Power.
Existing solar battery is mainly by monocrystalline silicon and hull cell and third generation high performance solar batteries.For monocrystalline
Silion cell, its preparation process is extremely complex, and the prices of raw materials are expensive, and power conversion efficiency is also close to theoretical limit.The second generation
It is easy to process for the solar battery of thin-film technique preparation, it is low in cost, it can be achieved that device collection on glass and flexible base board
At.But compound therein be easy in air with the substance reactions oxygenolysis such as oxygen gas and water, further, since use environment
It is exposed under sunlight irradiation, exacerbates the progress of decomposition reaction, battery life is had a greatly reduced quality.Third generation solar cell it is excellent
Point: safe and reliable, high efficiency, film, material enrich.Although still in the exploratory stage, the development of third generation solar cell
Fast speed, development potentiality are larger.Such as perovskite solar battery (PVSCs), dye-sensitized solar cells, organic solar
Battery and nanocrystal solar cells are studying the production of industrialization, have high power conversion efficiency, but due to research side
The method that case is generally used spin coating, the device of preparation are also small area, and spin coating method is not suitable for the preparation of area battery,
The homogeneous film formation of large area is that a challenge is high, in addition, stability also must be guaranteed in glove box preparation process.
In conclusion problem of the existing technology is:
(1) prior art, can not large-scale commercial production due to its with high costs, complex process；
(2) stability is insufficient, and the service life is short；
(3) prior art prepare environment harshness, most of perovskite cell manufacturing process be full of nitrogen gloves
It is carried out in case；
(4) prior art can not also prepare the large area perovskite solar battery of uniform high-efficiency.
Solve the difficulty of above-mentioned technical problem:
(1) perovskite material itself and unstable, easily oxygenolysis in air, under high humility hyperoxic conditions such as
What guarantees it is crucial at fast filming while film uniformity；
(2) perovskite material is mostly toxic, and mating gas precautions are needed for operator；
(4) method that auxiliary heating was not used in forefathers when being coated with calcium titanium ore bed, heating temperature are needed with preparing
Journey and adjust；
(5) full blade coating, for the uniformity challenge pole of 100 square centimeters of solar energy in large area battery film forming
Greatly, skilled operation degree is required high.
Solve the meaning of above-mentioned technical problem:
(1) cost for significantly reducing the preparation of perovskite battery, is conducive to be commercialized；
(2) preparation method scratched entirely greatly simplifies preparation step, so that preparation is become convenient and efficient, is conducive to industry
Change；
(3) it ensure that the stability of battery, extend the service life, be conducive to improve battery practicability；
The battery of (4) 100 square centimeters of large area is conducive to be commercialized and improve practicability.
Summary of the invention
In view of the problems of the existing technology, the present invention provides the calcium titaniums that entirely prepared by blade coating printing under a kind of air conditions
Mine solar battery and method.
The invention is realized in this way a kind of method of the perovskite solar battery of full blade coating printing preparation includes:
Step 1, the glass baseplate coated with the tin oxide of detergent ultrasonic cleaning Fluorin doped；
Step 2 successively washes ionized water, acetone, isopropanol, then by the FTO substrate cleaned in advance in UV- ozone
Cleaning is in cleaner to improve contact of the PEDOT:PSS with substrate；
Step 3 by poly styrene sulfonate aqueous solution isopropanol and filters, then blade coating preparation film layer；
Step 4, by assisting heating means preparing perovskite thin film, perovskite precursor solution PbAc2·3H2O:MAI
Molar ratio be 1:3, filtered with filter, preheat, be then applied in substrate, the film obtained on ito glass；
Step 5, the coating of perovskite thin film boundary material and prepares electrode, obtains perovskite solar battery.
Further, in step 3, poly styrene sulfonate aqueous solution is used in combination with isopropanol with the dilution proportion of 1:3
The filtering of 0.45mm filter, then blade coating preparation film layer under the conditions of substrate temperature is 60 DEG C, then hot at 140 DEG C in air
Annealing 30 minutes, film layer PEDOT:PSS with a thickness of 40nm.
Further, in step 4, perovskite thin film preparation method: middle perovskite precursor solution PbAc2·3H2O): MAI's
Molar ratio is 1:3, uses 800mg/ml-10.45 μm of PTFE filter, 80 μ l filtering, preheats 15 minutes, then first at 90 DEG C
With 22mm under 130 DEG C of base reservoir temperature-1Gap blade blade with 90 μm is applied in substrate, is obtained on ito glass
Film is annealed 10 minutes at 90 DEG C.
Further, in step 5, prepared by the coating of perovskite thin film boundary material and electrode: in 60 DEG C of underlayer temperature
Under, 40 μm of PC is filtered with 0.45 μm of PTFE optical filter61BM chlorobenzene 20mg/mL filters 40 μm with 0.45 μm of PTFE optical filter
0.5mg/mL BCP solution, and successively scratch PC in perovskite film again61BM and BCP solution；Finally, by barn door in height
Vacuum 1 × 10-4The silver electrode that 150nm thickness is evaporated under Pa obtains battery device.
The BCP solution of mg/mL, and successively PC is scratched in perovskite film again61BM and BCP solution.Finally, being existed by barn door
High vacuum 1 × 10-4The silver electrode of 150nm thickness is evaporated under Pa.
Another object of the present invention is to provide scratch printing entirely under a kind of utilization air conditions to prepare perovskite too
The perovskite solar battery of the method preparation of positive energy battery.
Another object of the present invention is to provide a kind of domestic hot water's devices for being equipped with the perovskite solar battery.
Another object of the present invention is to provide a kind of public arena illuminations for being equipped with the perovskite solar battery
Equipment.
The environmentally protective motor-driven of the perovskite solar battery is installed another object of the present invention is to provide a kind of
Vehicle.
The grid-connected with power grid of the perovskite solar battery is installed another object of the present invention is to provide a kind of
Solar energy supply equipment group.
Another object of the present invention is to provide scratch printing entirely under a kind of implementation air conditions to prepare perovskite too
The perovskite solar battery large area of the method for positive energy battery prepares production line.
In conclusion advantages of the present invention and good effect are as follows:
The present invention provides technical support for the improved efficiency of prepare with scale large area perovskite solar cell device.
The present invention prepares large area perovskite solar battery in the method that can be printed completely in air, is scraped using heat auxiliary
Knife coating technique prepares perovskite solar battery using one-step method.Most important part is to control harsh air ring in the process
The pattern of perovskite thin film in border.Applied formant structure be using PEDOT:PSS as hole mobile material and
PC61Planar inverted structure of the BM as electron transport material.Since perovskite material is highly sensitive to water and oxygen, it is very
It is easy to decompose in air, therefore preparing high performance solar batteries in air environment is a huge challenge.In experiment with
Lead acetate trihydrate [(CH3COO)2Pb·3H2O] it is lead source, with methyl iodide amine [CH3NH3I, (MAI)] reaction generation perovskite
Light absorbent [CH3NH3PbI3].PEDOT:PSS is as hole transmission layer (HTL) and PC61BM as electron transfer layer (ETL).
Hole transmission layer, calcium titanium ore bed and electron transfer layer are prepared by scraper method respectively.Reach 30% or more ring in relative humidity
In border, by adjusting substrate temperature, the conditions such as annealing temperature and scraper plate spreading rate, in effective area 1cm2Under reach 10.0%
Maximum power conversion efficiency, and for 0.1cm2Effective area, energy conversion efficiency also reached 13%.It is aerial
Technology of preparing is not limited by glove box, makes it possible to see the production of large area, prepares skill especially for realization large area
Art puts into the manufacture taken on and provides the foundation.
Detailed description of the invention
Fig. 1 is the method for scratching printing under air conditions provided in an embodiment of the present invention entirely and preparing perovskite solar battery
Flow chart.
Fig. 2 is that SEM figure provided in an embodiment of the present invention carries out phenogram to the configuration of surface of perovskite thin film.
Fig. 3 is provided in an embodiment of the present invention by atomic force microscopy surface Morphological Characterization figure.
Fig. 4 is the UV-visible absorption spectrum of different perovskite thin films provided in an embodiment of the present invention.
Fig. 5 is provided in an embodiment of the present invention to be prepared in the case where relative humidity is more than 35% air conditions by knife coating
The X-ray diffraction spectra figure of perovskite film.
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 described herein, specific examples are only used to explain the present invention, is not used to limit
The fixed present invention.
In the prior art, first generation solar battery includes monocrystalline silicon and polysilicon solar cell, dominates photovoltaic at present
Market.Crystal silicon solar batteries have very big power conversion efficiency, but its preparation process is extremely complex, and the prices of raw materials are high
It is expensive, so that businessman is difficult to get a profit and apply government subsidy to support its business.Development for many years, power conversion efficiency almost reach
To theoretical value.Monocrystaline silicon solar cell has very big power conversion efficiency, but its preparation process is extremely complex, raw material
It is expensive.
Second solar battery prepared on behalf of thin-film technique, such as amorphous silicon and other inorganic compound thin film solar-electricities
Pond.Thin-film solar cells has preferable absorbability to the visible light of small thickness, easy to process, low in cost, can be real
Device on present glass and flexible base board is integrated, and compared with the silicon solar cells such as wearable device, they have opened up difference
Market.But its stability problem cannot also solve always.
In order to solve the above technical problems, below with reference to concrete scheme, the present invention is described in detail.
As shown in Figure 1, scratching printing under air conditions provided in an embodiment of the present invention entirely prepares perovskite solar battery
Method includes:
S101, the glass baseplate coated with the tin oxide of detergent ultrasonic cleaning Fluorin doped.
S102 successively washes ionized water, acetone, isopropanol, then that the FTO substrate cleaned in advance is clear in UV- ozone
Cleaning is in clean device to improve contact of the PEDOT:PSS with substrate.
S103 by poly styrene sulfonate aqueous solution isopropanol and is filtered, then blade coating preparation film layer.
S104, by assisting heating means preparing perovskite thin film, perovskite precursor solution PbAc2·3H2O:MAI's
Molar ratio is 1:3, is filtered with filter, and preheating is then applied in substrate, the film obtained on ito glass.
S105, the coating of perovskite thin film boundary material and prepares electrode, obtains perovskite solar battery.
In step S103, poly styrene sulfonate aqueous solution is filtered with the dilution proportion of 1:3 and with isopropanol with 0.45mm
Device filtering, then blade coating prepares film layer under the conditions of substrate temperature is 60 DEG C, and then thermal annealing 30 divides at 140 DEG C in air
Clock, film layer PEDOT:PSS with a thickness of 40nm.
In step S104, perovskite thin film preparation method: middle perovskite precursor solution PbAc2·3H2O): the molar ratio of MAI
For 1:3,800mg/ml is used-10.45 μm of PTFE filter, 80 μ l filtering, preheats 15 minutes first at 90 DEG C, then 130
DEG C base reservoir temperature under with 22mm-1Gap blade blade with 90 μm is applied in substrate, and the film obtained on ito glass exists
90 DEG C are annealed 10 minutes.
In step S105, prepared by the coating of perovskite thin film boundary material and electrode: under 60 DEG C of underlayer temperature, using
0.45 μm of PTFE optical filter filters 40 μm of PC61BM chlorobenzene 20mg/mL filters 40 μm with 0.45 μm of PTFE optical filter
The BCP solution of 0.5mg/mL, and successively PC is scratched in perovskite film again61BM and BCP solution.Finally, by barn door in Gao Zhen
Sky 1 × 10-4The silver electrode that 150nm thickness is evaporated under Pa obtains battery device.
In the present invention, it provides and a kind of prepares perovskite solar battery using scratching printing under the air conditions entirely
The perovskite solar battery of method preparation.
The invention will be further described combined with specific embodiments below.
Embodiment:
1 material:
Poly- (3,4- ethyldioxythiophene): poly styrene sulfonate (PEDOT:PSS) aqueous solution.Fluorine-doped tin oxide
(FTO) electro-conductive glass (side is 15 Ω sq), lead acetate trihydrate (PbAc2·3H2O).Methylpyridinium iodide ammonium (MAI), Diethylaminoethyl ammonium
(MABr) and [6,6]-phenyl-C61- methyl butyrate (PC61BM).Other solvents are purchased from Sigma-Aldrich company, these are commercially available
Material is directly employed without and is further purified, including n,N-Dimethylformamide (DMF), isopropanol, and chlorobenzene and dimethyl are sub-
Sulfone (DMSO).
2 experimental facilities:
X-ray diffraction.Automatic laboratory coater.Scanning electron microscope.Spin coater.UV cleaner；Glove box.Heat deposition
Machine；External quantum efficiency；Solar simulator.Ultraviolet/visible/near infrared spectrophotometer.
3 methods:
Step 1: the glass baseplate coated with the tin oxide (FTO) of detergent ultrasonic cleaning Fluorin doped.
Step 2: successively washing ionized water, acetone, isopropanol with 45 minutes, then the FTO substrate cleaned in advance exists
20 minutes are cleaned in UV- ozone cleaner to improve contact of the PEDOT:PSS with substrate.
Step 3: by hole transmission layer poly styrene sulfonate (PEDOT:PSS) aqueous solution isopropanol with the ratio of 1:3
It dilutes and 0.45mm filter is used to filter, then blade coating preparation film layer under the conditions of substrate temperature is 60 DEG C, then exists in air
Thermal annealing 30 minutes at 140 DEG C, the thickness of film layer PEDOT:PSS are about 40nm.
Step 4: by assisting heating means to prepare perovskite thin film (see figure under the environmental condition of RH ambient humidity 45%
SEM figure carries out phenogram to the configuration of surface of perovskite thin film there are five 2).
Step 5: perovskite precursor solution and perovskite thin film preparation method ((PbAc2·3H2O): the molar ratio of MAI is 1:
3, use 800m/ml-10.45 μm of PTFE filter, 80 μ l filtering) it is preheated 15 minutes first at 90 DEG C, then in 130 DEG C of base
With 22mm at a temperature of bottom-1Gap blade blade with 90 μm is applied in substrate.The film obtained on ito glass is moved back at 90 DEG C
Fire 10 minutes.
In embodiments of the present invention, prepared by the coating of perovskite thin film boundary material and electrode: in 60 DEG C of underlayer temperature
Under, 40 μm of PC is filtered with 0.45 μm of PTFE optical filter61BM chlorobenzene 20mg/mL filters 40 μm with 0.45 μm of PTFE optical filter
0.5mg/mL BCP solution, and successively scratch PC in perovskite film again61BM and BCP solution.Finally, by barn door in height
Vacuum 1 × 10-4The silver electrode of 150nm thickness is evaporated under Pa.
4 experimental facilities and characteristic:
With scanning electron microscope (SEM, TESCAN MIRA) under 5kV acceleration voltage to the pattern of perovskite thin film into
Row characterization.Olympus microscope (BX51) shoots optical imagery.Under the operating condition of 20kV and 30mA, by with CuK α
The diffractometer (D8Advance ECO) of radiation is with certain scan rate measurement crystal structure.The optical property of sample is being equipped with
It is measured on the UV/Vis/NIR spectrophotometer of integrating sphere (PerkinElmer Lambda 950).Using equipped with 300W xenon lamp
Solar simulator (Enlitech SS-F7-3A) with 2400 light source measurement instrument of Keithley is in mono- solar illumination of AM5G
(100mWcm-2) under measure J-V curve.Luminous intensity is adjusted by the silicon solar cell that NREL is calibrated.In measurement process
In, battery is 0.1-4cm by aperture2Mask covering.Using comprising xenon lamp, monochromator, for the Si detector of calibration and double
The EQE system (Enlitech QE-R3011) of channel power source measures external quantum efficiency (EQE) value.
Below with reference to coating parameter, the invention will be further described for perovskite precursor solution.
1) coating parameter:
The form of the perovskite thin film of solution processing is mainly determined by nucleation and crystal growth kinetics.It is best in order to obtain
The device of performance, needs to study and adjust several groundwork parameters, these parameters may seriously affect the shape of perovskite thin film
Looks.Firstly, the temperature of substrate can determine the rate of volatilization of solvent and the precipitation rate of crystal in blade coating.From crystal growth
Situation is seen, when solvent is volatilized, has more nuclearing centres.As a result, the quantity of crystal may be more, it means that brilliant
The crystallite dimension of body is smaller.On the contrary, nucleus has more times to grow up when solvent volatilization is slow.But rate of volatilization is too slow
Biggish projecting edge can be formed on domain boundary, this may will increase the roughness of superstructure and limit the diffusion of electronics.
As Fig. 3 passes through shown in atomic force microscopy surface Morphological Characterization figure, although the heating temperature of coated substrate is only 110
DEG C, but area size arrives greatly exceed 100 μm completely.These regions are extended to the outside from core center as radial pattern, along
Orientation can capture electronics to reduce the direction of current density with some apparent gullies.When underlayer temperature is 150 DEG C, at
Core rate makes very much domain sizes still very little fastly, in some instances it may even be possible to which length is large enough in conjunction with adjacent domains.As a result, surface coverage is very
Difference, there are many defects in perovskite thin film, cause short circuit and electronics captured, as shown in Fig. 3 (c).As intermediate state, when
The temperature of coated substrate be 130 DEG C (such as Fig. 3 (b)) when, these regions can sufficiently grow up and with adjacent domain be in close contact with
Reach relatively good configuration of surface.
Substrate needs specific heating temperature when in addition to carrying out scraper coating, and annealing temperature and time after coating also determine
Configuration of surface.Suitable annealing temperature and time can make domain grow up and exclude by Pb (CH3CO2)2·3H2What O was introduced
Water.But higher annealing temperature and time may make perovskite thin film crack, and are exposed in severe air and also can for a long time
Decompose perovskite material.
It is obvious that the clearance height between the top surface and coating blade of FTO substrate determines the thickness of perovskite thin film
Degree.Perovskite thin film with suitable thickness can not only absorb enough light as much as possible, but also can save former material
Material is to reduce cost and prevent the crackle of thick perovskite thin film.When the thickness of perovskite thin film is blocked up, in annealing process easily
In rupture, this may be a fatal defect.Other than clearance height, spreading rate also determines the thickness of perovskite thin film.
When the molar density of perovskite precursor solution is 1mmol/mL, as shown in Fig. 3 (e), when coating rate is 22mms-1When, calcium
The thickness of titanium ore film is about 600nm, and gap is 90 μm.The solution may flow back below scraper, if coating
Rate is very low, will lead to thickness increase.
In order to prepare HTL and ETL, the functional layer important as other two determines the optimal parameter for reaching peak efficiencies
It is also vital.The configuration of surface of perovskite film is determined especially as the HTL on calcium titanium ore bed basis.It must use up can
Can be thin, to absorb light as few as possible before perovskite thin film, thus effectively transporting holes.In this experiment,
I has used PEDOT:PSS as hole mobile material, because of some special reasons.PEDOT:PSS is a kind of stable gathers
Object is closed, it is water-soluble.As a kind of aqueous solution, since it influences the harm of glove box, it is not suitable in glove box
Operation.However, PEDOT:PSS can be applied as a kind of polymer on a flexible substrate, because it will not in bending apparatus
Cracking.For TiO2Layer, it is easy to open circuit occur and lead to short circuit.Furthermore the moderate cost of PEDOT:PSS, these successfully make
PEDOT:PSS is possibly realized as hole mobile material (such as roll-to-roll technology) potential in commercially producing.With spin coating HTL
It compares, the roughness of scraper coating HTL is bigger, as shown in Figure 3.What (d) proposed mean roughness about 10nm in Fig. 3 scrapes cutter painting
The configuration of surface of cloth HTL.In contrast, the average surface roughness of HTL spin-coating method is less than 2nm.In order to support this point, when
When coating perovskite thin film on both HTL, as shown in Fig. 3 (e), the average surface roughness of calcium titanium ore bed on spin coating HTL
Only 45.5nm, and for the HTL of blade coating, it is 66.7nm Fig. 3 (b).However, on calcium titanium ore bed
ETL, preparation process is not stringent, because it only needs to obtain good form to transmit electronics.
2) perovskite precursor solution:
As most important part, the composition of perovskite precursor solution be the key that determine surface and crystal habit because
Element.Different elements in perovskite may change crystal structure to influence its property, such as band gap, light abstraction width and heat resistance
Deng.The boiling temperature of DMF is 153 DEG C, it means that in coating process, DM F can quickly volatilize on 130 DEG C of substrate.
When the DMSO for being 189 DEG C by boiling point is added in solvent, evaporation rate can be reduced, and perovskite crystal will grow up, perovskite thin film
Surface topography become more much better than Fig. 3 (a), compared with Fig. 3 (b).DMSO will form interphase with precursor, to reduce film forming
PbAc in the process2With the too fast combination of organic group.When changing the percent by volume of DMSO doping in DMF, find 10%
DMSO incorporation is as can get best surface performance in the DMF of solvent, so that surface average roughness is dropped to from 157nm
66.7nm.Therefore, the peak power transfer efficiency of device rises to 8.41% from 5.96% in table 1.
As described above, the different halide ions being entrained in perovskite precursor solution can have different effects.Work as halogen
When the radius of element increases, perovskite material can have better stability.But for the halogen yin with maximum ion radius
The CH of ion3NHI3Perovskite material, the excessive adjustable band gap of Br ion being doped to as MABr in MAI.To doping percentage
Than being ranked up, the MABr of about 5% molar content of discovery can make up the MA as caused by thermally decomposing successfully as excess component+'s
Loss, leads to the increase about 0.74% of power conversion efficiency.Although CsBr can significantly improve the open-circuit voltage of device
1.15V, but due to the reduction of current density and fill factor, power conversion efficiency still has loss.
As shown in the UV-visible absorption spectrum of Fig. 4 difference perovskite thin film, absorption spectrum holds perovskite solar-electricity
Br in pond-With CsBr doping process.Doping can effectively increase the absorption of short-wavelength light, and band gap increases.
Fig. 4 shows that the X of the perovskite film prepared in the case where relative humidity is more than 35% air conditions by knife coating is penetrated
Line difraction spectrum.It is well known that water can decompose perovskite material, but from the point of view of XRD result, heat auxiliary scraper plate paint-on technique can
To manufacture the perovskite solar cell device that the feature peak intensity of perovskite material is relatively strong and has excellent performance.
The X-ray of the perovskite film prepared from Fig. 5 in the case where relative humidity is more than 35% air conditions by knife coating is spread out
It penetrates in spectrogram as can be seen that PbAc2·3H2The source O perovskite thin film has (002) and (110) crystal face for being parallel to substrate.This
It is a little the result shows that, PbAc2·3H2The water of hydrate in O helps to create height-oriented perovskite thin film.For PbI2, special
Sign peak is relatively weak compared with Fig. 5, it means that the decomposition of perovskite material is seldom positioned at 12.6 °.After medium annealing process,
Moisture in PbAc23H2O and air can be escaped effectively from perovskite material, it means that device performance is good.Table
1 is completely printable perovskite solar battery 1cm at different conditions2Peak efficiencies in the air of effective area
Table 1
Below with reference to effect, the invention will be further described.
The present invention prepares large area perovskite solar battery in the method that can be printed completely in air, is scraped using heat auxiliary
Knife coating technique prepares perovskite solar battery using one-step method.Most important part is in harsh air environment in the process
The pattern of middle control perovskite thin film.Applied formant structure be using PEDOT:PSS as hole mobile material and
PC61Planar inverted structure of the BM as electron transport material.Since perovskite material is highly sensitive to water and oxygen, it is very
It is easy to decompose in air, therefore preparing high performance solar batteries in air environment is a huge challenge.In experiment with
Lead acetate trihydrate [(CH3COO)2Pb·3H2O] it is lead source, with methyl iodide amine [CH3NH3I, (MAI)] reaction generation perovskite
Light absorbent [CH3NH3PbI3].PEDOT:PSS is as hole transmission layer (HTL) and PC61BM is as electron transfer layer (ETL).It is empty
Cave transport layer, calcium titanium ore bed and electron transfer layer are prepared by scraper method respectively.Reach 30% or more environment in relative humidity
In, by adjusting leaf temperature, the conditions such as annealing temperature and scraper plate spreading rate, in effective area 1cm2Under reach 10.0% most
High power conversion efficiency, and for 0.1cm2Effective area, energy conversion efficiency also reached 13%.Aerial system
Standby technology is not limited by glove box, makes it possible to see the production of large area, especially for realization large area technology of preparing
It provides the foundation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. the method that printing prepares perovskite solar battery is scratched under a kind of air conditions entirely, which is characterized in that the air
Under the conditions of scratch the method that printing prepares perovskite solar battery entirely and include:
Step 1, the glass baseplate coated with the tin oxide of detergent ultrasonic cleaning Fluorin doped；
Step 2 successively washes ionized water, acetone, isopropanol, then by the FTO substrate cleaned in advance in UV- ozone clean
Cleaning is in device to improve contact of the PEDOT:PSS with substrate；
Step 3 by poly styrene sulfonate aqueous solution isopropanol and filters, then blade coating preparation film layer；
Step 4, by assisting heating means preparing perovskite thin film, perovskite precursor solution PbAc2·3H2O:MAI's rubs
You are filtered with filter than being 1:3, preheat, be then applied in substrate, the film obtained on ito glass；
Step 5, the coating of perovskite thin film boundary material and prepares electrode, obtains perovskite solar battery.
2. the method that printing prepares perovskite solar battery is scratched under air conditions as described in claim 1 entirely, feature
It is, in step 3, by poly styrene sulfonate aqueous solution isopropanol with the dilution proportion of 1:3 and with 0.45mm filter mistake
Filter, then blade coating preparation film layer under the conditions of substrate temperature is 60 DEG C, then thermal annealing 30 minutes at 140 DEG C in air,
Film layer PEDOT:PSS with a thickness of 40nm.
3. the method that printing prepares perovskite solar battery is scratched under air conditions as described in claim 1 entirely, feature
It is, in step 4, perovskite thin film preparation method: middle perovskite precursor solution PbAc2·3H2O): the molar ratio of MAI is 1:
3, use 800mg/ml-10.45 μm of PTFE filter, 80 μ l filtering, preheats 15 minutes first at 90 DEG C, then at 130 DEG C
With 22mm under base reservoir temperature-1Gap blade blade with 90 μm is applied in substrate, and the film obtained on ito glass is at 90 DEG C
Annealing 10 minutes.
4. the method that printing prepares perovskite solar battery is scratched under air conditions as described in claim 1 entirely, feature
It is, in step 5, prepared by the coating of perovskite thin film boundary material and electrode: under 60 DEG C of underlayer temperature, with 0.45 μm
PTFE optical filter filter 40 μm of PC61BM chlorobenzene 20mg/mL filters 40 μm of 0.5mg/mL with 0.45 μm of PTFE optical filter
BCP solution, and successively scratch PC in perovskite film again61BM and BCP solution；Finally, by barn door in high vacuum 1 × 10- 4The silver electrode that 150nm thickness is evaporated under Pa obtains battery device.
5. it is a kind of using scratched entirely under air conditions described in claim 1 printing prepare perovskite solar battery method prepare
Perovskite solar battery.
6. a kind of domestic hot water's device for being equipped with perovskite solar battery described in claim 5.
7. a kind of public arena lighting apparatus for being equipped with perovskite solar battery described in claim 5.
8. a kind of environmentally protective motor vehicles for being equipped with perovskite solar battery described in claim 5.
9. a kind of solar energy supply equipment grid-connected with power grid for being equipped with perovskite solar battery described in claim 5
Group.
10. a kind of method implemented to scratch under air conditions printing entirely described in claim 1 and prepare perovskite solar battery
Perovskite solar battery large area prepares production line.
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| CN112002805A (en) * | 2020-08-04 | 2020-11-27 | 南方科技大学 | Knife coating equipment |
| CN115996583A (en) * | 2023-03-24 | 2023-04-21 | 西安电子科技大学 | Perovskite/silicon laminated solar cell and preparation method thereof |
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| CN115996583A (en) * | 2023-03-24 | 2023-04-21 | 西安电子科技大学 | Perovskite/silicon laminated solar cell and preparation method thereof |
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