CN108428797B - A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology - Google Patents
A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology Download PDFInfo
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Abstract
The preparation method for the flexible large area perovskite solar cell based on roller coating technology that the invention discloses a kind of, comprising the following steps: one, processing flexible conductive substrates；Two, electron transfer layer, perovskite absorbed layer, hole transmission layer are sequentially prepared on flexible conductive substrates using roller coating technology, or hole transmission layer, perovskite absorbed layer, electron transfer layer are sequentially prepared on flexible conductive substrates using roller coating technology；Three, top electrode and hearth electrode are prepared, perovskite solar cell is made.The present invention can effectively solve that flexible substrate is easily-deformable, perovskite crystalline is of poor quality and the technical problems such as uneven thickness by adjusting roller coating technology parameter；Plated film homogeneity and planarization are improved, the preparation of flexible especially large area perovskite solar cell may be implemented, expanded the application scenarios of perovskite solar cell；This method is expected to really realize quick, low cost, roll-to-roll production large area perovskite battery on flexible substrates.
Description
Technical field
The present invention relates to perovskite solar cell technical field, specifically a kind of flexible large area calcium based on roller coating technology
The preparation method of titanium ore solar cell.
Background technique
From 2009, perovskite solar cell achieved rapid development, the photoelectricity of the perovskite solar cell of rigid substrate
Transfer efficiency alreadys exceed 22%, and the photoelectric conversion efficiency of flexible substrate perovskite solar cell alreadys exceed 16%.
Currently, in the preparation of perovskite battery, still based on nonbreakable glass substrate, because of its surfacing, the calcium titanium of preparation
Mine battery repeatability is high, but glass substrate has the shortcomings that frangible, weight is heavy, can not be bent, the scene limited its application.It is soft
Property substrate perovskite solar cell have many advantages, such as impact resistance, light-weight, flexible, easy to carry, being suitble to develop flexibility can
Wearable device.But most flexible substrate perovskite batteries still use produced in conventional processes, such as spin-coating method, and conventional method is only fitted
The method for closing the production of laboratory small area, it is difficult to applied to the industrial production of broad area device, and the effective rate of utilization of material
It is low, serious waste of resources.In addition flexible substrate surface irregularity, there is convex-concave, substrate discontinuity equalization in conventional method, when coating
It is easily-deformable, the defects of leading to perovskite crystalline of poor quality, uneven thickness, it is difficult to realize roll-to-roll large area production.Therefore how
Prepare that thickness is uniform, the functional layer of smooth densification is to prepare one of the difficult point of high-efficiency soft solar cell.
Summary of the invention
The preparation for the flexible large area perovskite solar cell based on roller coating technology that the purpose of the present invention is to provide a kind of
Method, the present invention can effectively solve that flexible substrate is easily-deformable, perovskite crystalline is of poor quality and thickness by adjusting roller coating technology
Unequal technical problem；Plated film homogeneity and planarization are improved, flexible especially large area perovskite solar cell may be implemented
Preparation, expanded the application scenarios of perovskite solar cell；This method be expected to really realize it is quick on flexible substrates, low at
Originally, roll-to-roll production large area perovskite battery.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, comprising the following steps:
One, flexible conductive substrates are handled: by clean flexible conductive substrates at UV ozone processing or oxygen plasma
Reason；
Two, electron transfer layer, perovskite absorbed layer, hole transport are prepared on flexible conductive substrates using roller coating technology
Layer；Roll coating speeds are 1-100 mm/second；
Three, top electrode and hearth electrode are prepared, perovskite solar cell is so made.
As a further solution of the present invention: the flexible substrate is the thin polymer film for being coated with ITO or FTO, metal liner
Bottom, the combined substrate of metal/oxide, willow glass/ITO substrate, metal-based fibers substrate or paper substrate.Be coated with ITO or
The thin polymer film of FTO: such as polyethylene naphthalate (PET), polyethylene naphthalate (PEN), polyimides
Material, polyetheretherketonematerials materials etc.；Metal substrate: such as titanium, stainless steel, nickel, copper.
As a further solution of the present invention: electron transfer layer are as follows: titanium dioxide (TiO2), stannic oxide (SnO2), oxidation
Zinc (ZnO), fullerene derivate (such as PCBM), graphene, zinc-tin oxide, metal phthalocyanine molecular material, fullerene, in chromium oxide
One kind；
Hole transmission layer are as follows: nickel oxide (NiO), poly- (3,4-rthylene dioxythiophene)-poly styrene sulfonate (such as PEDOT:
PSS), poly styrene sulfonate (such as PSSA), cuprous sulfocyanide, 4- butyl-N, N- diphenylaniline homopolymer (Poly-TPD),
Two fluorenes (Spiro-OMeTAD) of 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, poly- [bis- (4- benzene
Base) (2,4,6- trimethylphenyl) amine] (PTAA), tetra- cyanogen dimethyl-parabenzoquinone (F4- of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-
TCNQ), one of polyvinylcarbazole (PVK).
As a further solution of the present invention: perovskite absorbed layer being prepared using a step rolling method in step 2: being prepared
PbX2, AZ mixed solution to get perovskite precursor solution is arrived, roller coating perovskite precursor solution, nitrogen stream is blown after roller coating
It is dry, it anneals 5-20 minutes under the conditions of 50-200 DEG C, obtains perovskite absorbed layer；
Wherein X is at least one of chloride ion, bromide ion, iodide ion and carboxylic acid ion, Z be chloride ion, bromide ion,
At least one of iodide ion, A be Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation in extremely
Few one kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, N-Methyl pyrrolidone, second
One of nitrile, isopropanol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes are a variety of.It is furthermore preferred that preparing calcium
When titanium ore precursor solution, in PbX2, ion solution additive MY is added in AZ mixed solution；A and M be Organoalkyl amine salt sun from
At least one of son, Organoalkyl amidine salt cation and alkali family cation；Y is carboxylic acid ion.
As a further solution of the present invention: preparing perovskite absorbed layer using two step rolling methods in step 2: first roller coating
One layer of PbX2Solution, roller coating AZ solution, nitrogen stream dry up again after drying, anneal 5-20 minutes, obtain under the conditions of 50-200 DEG C
Perovskite absorbed layer；
Wherein X is at least one of chloride ion, bromide ion, iodide ion and carboxylic acid ion, Z be chloride ion, bromide ion,
At least one of iodide ion, A be Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation in extremely
Few one kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, N-Methyl pyrrolidone, second
One of nitrile, isopropanol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes are a variety of.It is furthermore preferred that in PbX2
Ion solution additive MY is added in solution and/or AZ solution；A and M be Organoalkyl cationic amine salt, Organoalkyl amidine salt sun from
At least one of son and alkali family cation；Y is carboxylic acid ion.
As a further solution of the present invention: the hearth electrode and top electrode are ito transparent electrode, FTO transparent electrode, gold
Belong to nano wire oxide mixed transparent electrode, metal and oxide multilevel structure transparent electrode, alloy, metal electrode, carbon material
One of electrode；The preparation method of hearth electrode and top electrode is using roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, narrow
Stitch one of coating, silk-screen printing, printing, electron beam evaporation, chemical vapor deposition method.
As a further solution of the present invention: the regular groove of roller coating technology roller surfaces, trench depth 0-
500 microns, the density of groove is 1-10/millimeter, and roller uses corrosion-resistant, inertia material.The present invention is by adjusting molten
Liquid concentration, roll coating speeds, the trench depth of roller surfaces and density adjust wet-film thickness.
As a further solution of the present invention: being sequentially prepared electron transfer layer, calcium in step 2 on flexible conductive substrates
Titanium ore absorbed layer, hole transmission layer, the electron transfer layer are dried or are blown the preparation method comprises the following steps: the direct roller coating layer material solution
100-200 after dryoIt anneals 10-30 minutes under C；The hole transmission layer is done the preparation method comprises the following steps: the direct roller coating layer material solution
Dry or drying.
As a further solution of the present invention: being sequentially prepared hole transmission layer, calcium in step 2 on flexible conductive substrates
Titanium ore absorbed layer, electron transfer layer；The hole transmission layer is dried or is blown the preparation method comprises the following steps: the direct roller coating layer material solution
100-200 after dryoIt anneals 10-30 minutes under C；The electron transfer layer is done the preparation method comprises the following steps: the direct roller coating layer material solution
Dry or drying.Compared with prior art, the beneficial effects of the present invention are:
1. the present invention prepares perovskite battery using roller coating technology on flexible substrates, this method is easy to operate, production is imitated
Rate is high, so that perovskite battery preparation technique is more compatible, is really suitble to roll-to-roll production large area flexible perovskite battery.
2. the contact squeeze effect in roller coating process due to roller makes rough flexible substrate become smooth, prevents from serving as a contrast
Bottom deformation.
3. the present invention during preparing perovskite absorbed layer, is handled without toxic anti-solvent, is reduced in preparation process
Toxic hazard and process complexity, more industrial application potentiality.
4. the trench depth of roller surfaces and density can effectively control film thickness in the present invention, traditional system is overcome
The shortcomings that perovskite crystalline is of poor quality caused by flexible substrate is easily deformed during standby, uneven thickness.
5. rolling method uses in the present invention electron transfer layer or hole transmission layer solution and perovskite precursor solution etc.
The effective rate of utilization of material is about 95%, much higher than 10% or so utilization rate of the conventional methods such as spin-coating method, overcomes traditional work
In skill the shortcomings that waste of material, battery production cost is greatlyd save.
Detailed description of the invention
Fig. 1 is one of the structural schematic diagram of n-i-p type flexibility perovskite battery.
Fig. 2 is the second structural representation of p-i-n type flexibility perovskite battery.
Fig. 3 is that rolling method prepares film schematic diagram.
Fig. 4 is the structural schematic diagram of roller used in rolling method.
Wherein 1- top electrode；2- hole transmission layer；3- perovskite absorbed layer；4- electron transfer layer；5- flexible conductive substrates；
6- hearth electrode.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment 1
Please refer to Fig. 1 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Processing ITO flexible substrate (PET): clean flexible conductive substrates are handled with UV ozone；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology: addition SnO2Nano particle aqueous solution is stood
That is at the uniform velocity roller coating (as shown in Figure 3), and dried up with nitrogen stream, it anneals 30 minutes at 100 DEG C, electron transfer layer 4 is made；
Prepare CH3NH3I and PbI2Mixed solution, PbI2Concentration be 0.5 mol/L, solvent use dimethyl formyl
Amine, PbI2And CH3NH3I molar ratio is 1:1, and perovskite precursor solution is made, it is molten that above-mentioned mixing is added dropwise on the electron transport layer
Liquid is at the uniform velocity coated with immediately and is dried up with nitrogen stream, annealed 10 minutes at 100 DEG C, and perovskite absorbed layer is made；The present embodiment
In, roll coating speeds are 10-20 mm/second, and the trench depth of roller coating roller is 300 microns, density is 6 groove/millimeters；
Then roller coating Spiro-OMeTAD solution is at the uniform velocity coated with and is dried up with nitrogen stream, and hole transmission layer is made；
Finally vapor deposition gold obtains n-i-p type flexibility perovskite solar cell (Fig. 1) to electrode；It is soft in roller coating process
Property substrate is fixed on objective table, and roller coating process remains a constant speed coating.
Embodiment 2
Please refer to Fig. 1 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Processing stainless steel lining bottom: clean flexible conductive substrates are handled with UV ozone；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology: addition nano-titanium dioxide (TiO2) molten
Liquid, at the uniform velocity roller coating (as shown in Figure 3) immediately, and dried up with nitrogen stream, it anneals 10 minutes at 200 DEG C, electron transfer layer is made
4；
Prepare CH3NH3I and PbCl2Mixed solution, PbCl2Concentration be 1 mol/L, then add precursor solution
Wherein A is ethyl dimethylamine salt cation to the ion solution additive MY(of 10wt%, and Y is formate ion；CH3NH3I and PbCl2Rub
, than being 3:1, solvent is dimethylformamide and water, volume ratio 20:1 for you), CH is added dropwise on the electron transport layer3NH3I、PbCl2With
The mixed solution of ion solution additive MY is at the uniform velocity coated with immediately and is dried up with nitrogen stream, annealed 5 minutes at 200 DEG C, and calcium is made
Titanium ore absorbed layer；In the present embodiment, roll coating speeds are 30-40 mm/second, and the trench depth of roller coating roller is 50 microns, dredges
Density is 10 groove/millimeters；
Then poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] (PTAA) solution of roller coating, at the uniform velocity coating and low temperature are dry
It is dry, hole transmission layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metallic silver to electrode；Hearth electrode and top electrode
Preparation method can use evaporation, obtain flexible perovskite solar cell；Flexible substrate is fixed on load in roller coating process
On object platform, roller coating process remains a constant speed coating.
Embodiment 3
Please refer to Fig. 1 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Handle polyethylene naphthalate (PEN) flexible substrate: by clean flexible conductive substrates oxygen plasma
Processing；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology: addition nano-ZnO solution, immediately at the uniform velocity roller
It applies (as shown in Figure 3), and is dried up with nitrogen stream, annealed 20 minutes at 110 DEG C, electron transfer layer 4 is made；
Compound concentration is the PbBr of 1 mol/L2Solution adds the ion solution additive MY(of 0.1wt% wherein, and M is methyl
Amidine salt cation, Y are propionate ion, and solvent is N-Methyl pyrrolidone).One layer of PbBr of first roller coating2With the mixed solution of MY,
After spontaneously drying, then roller coating concentration is 0.5 mol/L carbonamidine bromine solutions (solvent is N-Methyl pyrrolidone), and nitrogen stream is blown
It is dry, it anneals 20 minutes under the conditions of 50 DEG C, can be prepared by perovskite absorbed layer；In the present embodiment, roll coating speeds be 20-30 millimeters/
Second, the trench depth of roller coating roller is 300 microns, density is 5 groove/millimeters；
Then roller coating 4- butyl-N, N- diphenylaniline homopolymer (Poly-TPD) solution, is at the uniform velocity coated with and uses nitrogen stream
Hole transmission layer is made in drying；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are carbon material electrode；The system of hearth electrode and top electrode
Preparation Method can use silk-screen printing, obtain flexible perovskite solar cell；Flexible substrate is fixed on load in roller coating process
On object platform, roller coating process remains a constant speed coating.
Embodiment 4
Please refer to Fig. 1 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Handle polyimide material flexible substrate: by clean flexible conductive substrates oxygen plasma treatment；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology: addition graphene solution, immediately at the uniform velocity roller
It applies (as shown in Figure 3), and with low temperature drying, then anneals 15 minutes at 130 DEG C, obtained electron transfer layer 4；
Prepare CH3NH3I, carbonamidine iodine, PbI2Mixed solution, PbI2Concentration be 1 mol/L, obtain precursor solution,
The ion solution additive MY(M for adding precursor solution 50wt% is propyl methylamine salt cation, and Y is acetate ion；CH3NH3I、
Carbonamidine iodine, PbI2Molar ratio be 9:1:10, solvent be dimethylformamide and dimethyl sulfoxide mixture, volume ratio 20:
1)；Above-mentioned mixed solution is added dropwise on the electron transport layer, at the uniform velocity roller coating and is dried up immediately with nitrogen stream, anneals 5 points at 130 DEG C
Perovskite absorbed layer is made in clock；In the present embodiment, roll coating speeds are 70-100 mm/second, and roller coating is smooth surface with roller；
Then roller coating PSSA solution is at the uniform velocity coated with and is dried up with nitrogen stream, and hole transmission layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metal nanometer line oxide mixed transparent electrode；
The preparation method of hearth electrode and top electrode can use magnetron sputtering, obtain flexible perovskite solar cell；In roller coating process
Middle flexible substrate is fixed on objective table, and roller coating process remains a constant speed coating.
Embodiment 5
Please refer to Fig. 2 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Processing ITO flexible substrate (PET): clean flexible conductive substrates are handled with UV ozone；
PTAA solution is added dropwise on flexible conductive substrates, immediately at the uniform velocity roller coating (as shown in Figure 3), and is dried up with nitrogen stream,
It anneals 10 minutes at 100 DEG C, hole transmission layer 2 is made；
Prepare CH3NH3I, lead acetate, PbI2Mixed solution, CH3NH3The concentration of I is 0.8 mol/L, adds solution
Wherein M is methyl methylamine salt cation to the ion solution additive MY(of 0.1wt%, and Y is formate ion；CH3NH3I, lead acetate,
PbI2Molar ratio be 10:2:7, solvent be dimethyl sulfoxide, gamma-butyrolacton mixture, volume ratio 3:2), in hole transmission layer
It is upper that above-mentioned mixed solution is added dropwise, it at the uniform velocity roller coating and is dried up with nitrogen stream, anneal 8 minutes at 120 DEG C later immediately, obtained perovskite
Absorbed layer；In the present embodiment, roll coating speeds are 1-20 mm/second, and the trench depth of roller coating roller is 100 microns, density
For 10 groove/millimeters；
Then PCBM solution is added dropwise in roller coating electron transfer layer, as shown in figure 3, being at the uniform velocity coated with and being dried up with nitrogen stream, In
It anneals 15 minutes at 120 DEG C, electron transfer layer is made；
Finally for vapor deposition gold to electrode, the preparation method of hearth electrode and top electrode can use magnetron sputtering method, obtain p-
I-n type flexibility perovskite solar cell (such as Fig. 2)；Flexible substrate is fixed on objective table in roller coating process, and roller coating process is protected
It holds and is at the uniform velocity coated with.
Embodiment 6
Please refer to Fig. 2 and Fig. 3-4, a kind of preparation side of the flexible large area perovskite solar cell based on roller coating technology
Method, comprising the following steps:
Processing polyetheretherketonematerials materials flexible substrate: clean flexible conductive substrates are handled with UV ozone；
PEDOT:PSS solution is added dropwise on flexible conductive substrates, immediately at the uniform velocity roller coating (as shown in Figure 3), anneals at 110 DEG C
10 minutes, hole transmission layer 2 is made；
Prepare CH3NH3I、CH3NH3Br and PbI2Mixed solution, PbI2Concentration be 0.4 mol/L (wherein,
CH3NH3I、CH3NH3Br and PbI2Molar ratio be 8:2:10, solvent be gamma-butyrolacton, N-Methyl pyrrolidone mixture,
Volume ratio 4:1), above-mentioned mixed solution is added dropwise on the hole transport layer, immediately at the uniform velocity coating and low temperature drying, moves back at 90 DEG C later
Perovskite absorbed layer is made in fire 15 minutes；In the present embodiment, roll coating speeds are 50-70 mm/second, the groove of roller coating roller
Depth is 400 microns, density is 2 groove/millimeters；
Then PCBM solution is added dropwise, dosage is 1-10 microlitres/square centimeter, as shown in figure 3, at the uniform velocity roller coating and with quiet immediately
Drying is set, electron transfer layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metal and oxide multilevel structure transparent electrode；
The preparation method of hearth electrode and top electrode (can also can be replaced printing, electron beam evaporation or chemical vapor deposition using sputtering method
The methods of product), obtain flexible perovskite solar cell；Flexible substrate is fixed on objective table in roller coating process, roller coating mistake
Journey remains a constant speed coating.
In embodiment, the thickness of perovskite absorbed layer can pass through perovskite precursor solution concentration, roll coating speeds (1-
100 mm/seconds) and the trench depth (0-500 microns) and density (1-10 groove/millimeter) of roller coating roller control
(such as Fig. 4)；
In above-described embodiment, electron transfer layer can be with are as follows: zinc-tin oxide, metal phthalocyanine molecular material, fullerene, oxidation
Chromium；Hole transmission layer are as follows: nickel oxide (NiO), tetra- cyanogen dimethyl-parabenzoquinone (F4-TCNQ) of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-,
Polyvinylcarbazole (PVK)；
Hearth electrode and top electrode may be replaced by ito transparent electrode, FTO transparent electrode, alloy electrode, according to electric polarity
Matter can choose using roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, slot coated, silk-screen printing, printing, electron beam
The methods of evaporation, chemical vapor deposition method preparation.
In above-described embodiment, it also can be replaced following solvents when preparing perovskite precursor solution: acetonitrile, isopropanol, second
Alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (9)
1. a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, which is characterized in that including with
Lower step:
One, flexible conductive substrates are handled: by clean flexible conductive substrates UV ozone processing or oxygen plasma treatment；
Two, electron transfer layer, perovskite absorbed layer, hole transmission layer are prepared on flexible conductive substrates using roller coating technology；Roller
Painting speed is 1-100 mm/second；
Three, top electrode and hearth electrode are prepared, perovskite solar cell is so made；
The regular groove of roller coating technology roller surfaces, trench depth are 0-500 microns；The density of groove is 1-10
A/millimeter.
2. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, perovskite absorbed layer is prepared using a step rolling method in step 2: preparing PbX2, AZ mixed solution to get arriving
Perovskite precursor solution, roller coating perovskite precursor solution, nitrogen stream dries up after roller coating, and anneal 5-20 under the conditions of 50-200 DEG C
Minute, obtain perovskite absorbed layer；
Wherein X is at least one of chloride ion, bromide ion, iodide ion and carboxylic acid ion, Z be chloride ion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
One of propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes are a variety of.
3. the preparation method of the flexible large area perovskite solar cell according to claim 2 based on roller coating technology,
It is characterized in that, when preparing perovskite precursor solution, in PbX2, the ionic liquid addition of 0.1-50wt% is added in AZ mixed solution
Agent MY；M is at least one of Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation；Y is carboxylic acid
Radical ion.
4. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, prepares perovskite absorbed layer using two step rolling methods in step 2: one layer of PbX of first roller coating2Solution, it is dry after roller again
AZ solution is applied, nitrogen stream dries up, and anneals 5-20 minutes under the conditions of 50-200 DEG C, obtains perovskite absorbed layer；
Wherein X is at least one of chloride ion, bromide ion, iodide ion and carboxylic acid ion, Z be chloride ion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
One of propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes are a variety of.
5. the preparation method of the flexible large area perovskite solar cell according to claim 4 based on roller coating technology,
It is characterized in that, in PbX2The ion solution additive MY of 0.1-50wt% is added in solution and/or AZ solution；M is Organoalkyl amine salt
At least one of cation, Organoalkyl amidine salt cation and alkali family cation；Y is carboxylic acid ion.
6. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, the hearth electrode and top electrode are ito transparent electrode, FTO transparent electrode, metal nanometer line oxide mixed transparent
One of electrode, metal and oxide multilevel structure transparent electrode, alloy, metal electrode, carbon material electrode；
The preparation method of hearth electrode and top electrode uses roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, slot coated, silk
One of wire mark brush, printing, electron beam evaporation, chemical vapor deposition method.
7. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, the flexible conductive substrates are the thin polymer film for being coated with ITO or FTO, metal substrate, the group of metal/oxide
Close one of substrate, willow glass/ITO substrate, metal-based fibers substrate or paper substrate；
The electron transfer layer are as follows: titanium dioxide, stannic oxide, zinc oxide, fullerene derivate, graphene, zinc-tin oxide, gold
Belong to one of Phthalocyanine material, fullerene, chromium oxide；
Hole transmission layer are as follows: nickel oxide, poly- (3,4-rthylene dioxythiophene)-poly styrene sulfonate, poly styrene sulfonate, sulphur
Cyanic acid is cuprous, 4- butyl-N, N- diphenylaniline homopolymer, 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino]-
Two fluorenes of 9,9'- spiral shell, poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine], tetra- cyanogen two of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-
One of methyl-p-benzoquinone, polyvinylcarbazole.
8. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, is sequentially prepared electron transfer layer, perovskite absorbed layer, hole transmission layer in step 2 on flexible conductive substrates,
The electron transfer layer is the preparation method comprises the following steps: the direct roller coating layer material solution, 100-200 after dry or dryingoAnneal 10- under C
30 minutes；The hole transmission layer is the preparation method comprises the following steps: the direct roller coating layer material solution, dry or drying.
9. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, is sequentially prepared hole transmission layer, perovskite absorbed layer, electron transfer layer in step 2 on flexible conductive substrates；
The hole transmission layer is the preparation method comprises the following steps: the direct roller coating layer material solution, 100-200 after dry or dryingoAnneal 10- under C
30 minutes；The electron transfer layer is the preparation method comprises the following steps: the direct roller coating layer material solution, dry or drying.
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