CN110224069A - A kind of perovskite solar battery and preparation method thereof with water-proof function - Google Patents
A kind of perovskite solar battery and preparation method thereof with water-proof function Download PDFInfo
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- H10K71/10—Deposition of organic active material
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Abstract
The invention discloses a kind of perovskite solar battery and preparation method thereof with water-proof function, method includes: to be sequentially prepared each functional layer on substrate；Ionic liquid layer is prepared in outermost functional layer, wherein the material of ionic liquid layer is the functional group that cation has hydrophobic property, and branch terminals contain C=C double bond, and ionic liquid anion is halogen element ion I‑、Br‑、Cl‑And F‑One of ionic liquid；Metal electrode is prepared in ionic liquid layer, obtains the perovskite solar battery.The present invention utilizes the ionic liquid with C=C double bond to heat the property polymerizeing in air, one layer of netted ionic liquid can be formed in perovskite solar cell surface, in addition the characteristic that ionic liquid is hydrophobic, it can play the role of surface waterproofing, to significantly improve the anti humility performance of perovskite solar cell.In surface depositing ions liquid, will not block charge transmission, so that the decaying of perovskite conversion efficiency of solar cell will not be caused.
Description
Technical field
The invention belongs to photovoltaic technology field, and in particular to a kind of perovskite solar battery with water-proof function and its
Preparation method.
Background technique
Perovskite solar cell is the latest generation thin film solar cell to be grown up based on dye-sensitized solar cells, with
By means of the advantage of high efficiency and low cost, by the extensive concern in worldwide.Perovskite solar cell certification at present is most
High efficiency has broken through 23%, can compare favourably with traditional silicon solar cell, industrial prospect is very considerable.However, perovskite
The instability problem of material becomes the maximum obstruction on its commercial applications road.It can cause perovskite material point all kinds of
In the factor of solution, water will be avoided strictly, deposited one layer of waterproof layer on perovskite solar cell surface, improved the moisture stable of battery
Property is particularly important.
Summary of the invention
To solve the above-mentioned problems, the preparation of the present invention provides a kind of perovskite solar battery with water-proof function
Method improves battery humidity stability.
The technical solution of the present invention is as follows: a kind of preparation method of the perovskite solar battery with water-proof function, comprising:
(1) it is sequentially prepared each functional layer on substrate；
(2) ionic liquid layer is prepared in outermost functional layer, wherein the material of ionic liquid layer has for cation
The functional group of hydrophobic property, and branch terminals contain C=C double bond, ionic liquid anion is halogen element ion I-、Br-、Cl-With
And F-One of ionic liquid；
(3) metal electrode is prepared in ionic liquid layer, obtains the perovskite solar battery.
Ionic liquid is a kind of green salts substances with many special natures, many kinds of, have thermal stability and
Chemical stability is high, can the advantages that operating temperature range is wide, conductive capability is strong, by designing the ionic liquid of different structure, it
Have many special physicochemical properties.Ionic liquid is made of organic cation and anion, some hydrophobic nonionic liquid
There are C=C double bond in organic cation structure of body, such ionic liquid is deposited on perovskite device surface in the present invention
When, under conditions of being contacted with air or mild heat, it may occur that polymerization reaction forms hydrophobic netted knot in device surface
Structure improves the moisture resistance of perovskite solar cell so as to play the role of waterproof.
Preferably, the substrate is FTO glass substrate, etched portions substrate first in the step (1), by substrate point
For etch areas and non-etch areas, electron-transport then is sequentially prepared on the partial region of etch areas and non-etch areas
Layer, perovskite absorbed layer and hole transmission layer.
Preferably, ionic liquid is dispersed in aqueous isopropanol in the step (2), it is prepared by spin-coating method
Ionic liquid layer.
Preferably, the concentration of the aqueous isopropanol is 1-5mg/mL, and when preparing ionic liquid layer by spin-coating method, drop
Add 30~100 microlitres of ionic liquids, spin speed is 3000~4000rpm, heats sample, temperature after the completion of spin coating in air
It is 40 DEG C~50 DEG C.
Preferably, the material of the electron transfer layer is TiO2, ZnO and SnO2In any one, the electronics passes
Defeated layer is prepared by sol-gal process, spray pyrolysis or magnetron sputtering method.
Preferably, it is ABX that the material of the perovskite absorbed layer, which is chemical formula,3The compound of type, wherein A be Cs, Rb,
CH3NH3And CH2(NH2)2At least one of, B Pb, X are one or both of I or Br；The perovskite absorbed layer is logical
Spin-coating method, thermal evaporation or knife coating is crossed to be prepared.
Preferably, the material of the hole transmission layer is the doping of bis- (trifluoro methylsulfonyl) imine lithiums (LITFSI)
Spiro-OMeTAD, institute's hole transmission layer are prepared by spin-coating method.
Preferably, the metal electrode is gold electrode, the metal electrode is prepared by thermal evaporation.
Preferably, the FTO glass substrate includes FTO transparency conducting layer, the edge of the ionic liquid layer is to downward
Cladding functional layer is stretched, and extends to FTO transparency conducting layer.
The present invention also provides a kind of preparation method preparations of above-mentioned perovskite solar battery with water-proof function
The obtained perovskite solar battery with water-proof function.
Compared with prior art, the beneficial effects of the present invention are embodied in:
(1) present invention, can be in calcium using having the ionic liquid of C=C double bond to heat the property polymerizeing in air
Titanium ore solar cell surface forms one layer of netted ionic liquid, in addition the characteristic that ionic liquid is hydrophobic, it is anti-to play surface
The effect of water can significantly improve the anti humility performance of perovskite solar cell.
(2) intermediate ion liquid itself of the present invention has good conductive property, therefore in surface depositing ions liquid,
Will not block charge transmission, so that the decaying of perovskite conversion efficiency of solar cell will not be caused.
(3) intermediate ion class of liquids of the present invention is various, and designability is strong, on the basis of the present invention can be further to similar
A possibility that ionic liquid of structure carries out structure optimization, obtains other performance boosts of device.
(4) present invention process is simple, at low cost, is suitble to future commercial applications.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the perovskite solar battery in the present invention with water-proof function.
Fig. 2 is the structural schematic diagram of ionic liquid.
Fig. 3 is battery J-V curve comparison figure.
Fig. 4 is that whether there is or not the battery of ionic liquid layer property test result figures stable in the air.
Fig. 5 is that whether there is or not the battery hydrophobic performance comparison diagrams of ionic liquid layer.
Specific embodiment
Embodiment 1
A kind of preparation method of perovskite solar cell, includes the following steps, as shown in Figure 1:
(1) using FTO electro-conductive glass as substrate 1, FTO electro-conductive glass has FTO transparency conducting layer 2 first with zinc powder and dilute
Hydrochloric acid reaction, etch away sections FTO are then cleaned by ultrasonic respectively using deionized water, ethyl alcohol, acetone, isopropanol, use nitrogen
After air-blowing is dry, places and handled 15 minutes in ozone clean machine.
(2) preparation for then carrying out electron transfer layer 3 first passes through spray pyrolysis and prepares one layer of fine and close TiO2Layer, first
Solution needed for preparing, 200 μ L bis- (levulinic ketone group) metatitanic acid diisopropyl esters are dissolved in 6mL isopropanol, are put into spraying nozzle,
It places the substrate above on 450 DEG C of flattening oven, is sprayed by spraying using oxygen nebulization, adjust the air-flow and jetting height of gas,
Solution is uniformly sprayed in substrate, continues 450 degree after injection and heats 30 minutes.After cooling to room temperature, sharp after taking-up
TiO is carried out with spin-coating method2The preparation of casing play, first by 1g TiO2Slurry is dissolved in 9mL ethyl alcohol, is stirred 12 hours.Take 50 μ L
Solution is added dropwise in the TiO prepared2In the substrate of compacted zone, 2000rpm spin coating 20 seconds, places and is heat-treated on flattening oven,
Heat treatment step is to be heated within room temperature 5 minutes 125 DEG C, is kept for 10 minutes, is heated within 5 minutes 250 DEG C, is kept for 10 minutes, 5 minutes
350 DEG C are heated to, is kept for 10 minutes, is heated within 5 minutes 450 DEG C, is kept for 10 minutes, is heated within 5 minutes 500 DEG C, is kept for 20 points
Terminate heat treatment after clock, after cooling to room temperature, immediately takes out and be put into glove box for use.
(3) preparation of calcium titanium ore bed 4 uses one-step method, progress perovskite precursor solution preparation first, by 1.5mmol iodine
Change lead and 1.5mmol CH3NH3I is added in dimethyl sulfoxide, and 60 DEG C are stirred 5 hours for use, by 60 μ L perovskite precursor solutions
It is added dropwise and is completely covered on TiO2On, after 2000rpm spin coating 12 seconds (acceleration 200rpm), 4000rpm high speed spin coating 30 seconds
(acceleration 3000rpm), the 20th second 110 μ L chlorobenzenes of dropwise addition of high speed, places substrate on warm table after spin coating, 100 DEG C
Heating 1 hour.
(4) preparation of hole transmission layer 5 is then carried out by spin-coating method, solution manufacturing method is, by 56.78mg
Spiro-OMeTAD is dissolved in 0.8mL chlorobenzene, then be added 14 μ L LiTFSI solution (acetonitrile solution of 520mg/mL) of dopant,
23.2 μ L Co (III) TFSI solution (acetonitrile solution of 300mg/mL) and 23.0 μ L tetra-tert pyridines.Hole transmission layer rotation
It is painted with, 30 μ L solution is taken to be added dropwise on calcium titanium ore bed, 4000rpm spin coating 30 seconds, hole transmission layer preparation was completed.
(5) preparation that ionic liquid layer 6 is carried out by spin-coating method, first by ionic liquid 1, bis- (4- vinyl benzyl) miaows of 3-
Azoles chloride (its structure is as shown in Figure 2) is dissolved in isopropanol, concentration 2mg/mL, and 30 μ L solution is taken to be added dropwise in hole transmission layer
On, 4000rpm spin coating 30 seconds, glove box is taken out after the completion of preparation, is heated 10 minutes for 50 DEG C in air.
(6) then, it wipes out extra part respectively with DMSO and acetonitrile, and is sent into the heat that thermal evaporation instrument carries out gold electrode
Evaporation preparation, gold electrode is with a thickness of 70nm or so.
Prepared battery J-V curve comparison is as shown in figure 3, when not preparing ionic liquid layer, cell photoelectric efficiency is
18.15%, short circuit current (Jsc), open-circuit voltage (Voc), fill factor (FF) be respectively 22.18mA/cm2, 1.064V,
76.9%；In preparation after ionic liquid layer, battery efficiency 17.91%, Jsc、Voc, FF be respectively 22.09mA/cm2, 1.057V,
76.7%, it has no and is substantially reduced, this indicates that ionic liquid layer does not influence the charge transport properties of battery.
When perovskite solar battery is placed in air, since the moisture in air can penetrate into perovskite material
Material, causes the decomposition of perovskite.Whether there is or not the battery of ionic liquid layer property test results stable in the air, as shown in figure 4, will not
The battery device for carrying out any encapsulation is placed in air, and humidity is 40% to 50%.It is bent that one group of J-V is tested at regular intervals
Line obtains each parameter of device and changes with time, it can be seen that after 1 month, has ionic liquid layer perovskite solar-electricity
Pond energy conversion efficiency still keeps the 90% of initial value, and the battery without ionic liquid layer only remains 23% starting efficiency,
This shows that the aerial stability of device is obviously improved after adding ionic liquid.
The present invention by carrying out the contact angle test of water to the perovskite solar cell that covers whether there is or not ionic liquid layer, thus
The hydrophobic performance on comparator device surface, as shown in figure 5, the surface contact angle that water and the device without ionic liquid layer covering are formed is
64.2 degree, and after adding ionic liquid layer, 96.3 degree of contact angle degree of being promoted to, this shows after ionic liquid layer deposits, shape
At hydrophobic reticular structure perovskite solar battery can be protected, prevent moisture from entering device, namely polymerize
Ionic liquid plays the role of waterproof layer.
Obviously, described embodiment is only section Example of the invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, should fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the perovskite solar battery with water-proof function characterized by comprising
(1) it is sequentially prepared each functional layer on substrate；
(2) ionic liquid layer is prepared in outermost functional layer, wherein the material of ionic liquid layer is cation with hydrophobic
The functional group of characteristic, and branch terminals contain C=C double bond, ionic liquid anion is halogen element ion I-、Br-、Cl-And F-
One of ionic liquid；
(3) metal electrode is prepared in ionic liquid layer, obtains the perovskite solar battery.
2. the preparation method of the perovskite solar battery with water-proof function as described in claim 1, which is characterized in that institute
Stating substrate is FTO glass substrate, and etched portions substrate first in the step (1) divides the substrate into etch areas and do not etch
Region, be then sequentially prepared on the partial region of etch areas and non-etch areas electron transfer layer, perovskite absorbed layer with
And hole transmission layer.
3. the preparation method of the perovskite solar battery with water-proof function, feature exist as claimed in claim 1 or 2
In ionic liquid is dispersed in aqueous isopropanol in the step (2), ionic liquid layer is prepared by spin-coating method.
4. the preparation method of the perovskite solar battery with water-proof function as claimed in claim 3, which is characterized in that institute
The concentration for stating aqueous isopropanol is 1-5mg/mL, and when preparing ionic liquid layer by spin-coating method, 30~100 microlitres of ionic liquids are added dropwise
Body, spin speed are 3000~4000rpm, heat sample after the completion of spin coating in air, and temperature is 40 DEG C~50 DEG C.
5. the preparation method of the perovskite solar battery with water-proof function as described in claim 1,2 or 4, feature exist
In the material of the electron transfer layer is TiO2, ZnO and SnO2In any one, the electron transfer layer is solidifying by colloidal sol
Glue method, spray pyrolysis or magnetron sputtering method are prepared.
6. the preparation method of the perovskite solar battery with water-proof function as described in claim 1,2 or 4, feature exist
In it is ABX that the material of the perovskite absorbed layer, which is chemical formula,3The compound of type, wherein A is Cs, Rb, CH3NH3And CH2
(NH2)2At least one of, B Pb, X are one or both of I or Br；The perovskite absorbed layer passes through spin-coating method, heat
Evaporation or knife coating are prepared.
7. the preparation method of the perovskite solar battery with water-proof function as described in claim 1,2 or 4, feature exist
In the material of the hole transmission layer is the Spiro-OMeTAD of bis- (trifluoro methylsulfonyl) imines lithium dopings, institute's hole transmission layer
It is prepared by spin-coating method.
8. the preparation method of the perovskite solar battery with water-proof function as described in claim 1,2 or 4, feature exist
In the metal electrode is gold electrode, and the metal electrode is prepared by thermal evaporation.
9. the preparation method of the perovskite solar battery with water-proof function as described in claim 1, which is characterized in that institute
Stating FTO glass substrate includes FTO transparency conducting layer, and the edge of the ionic liquid layer extends downwardly cladding functional layer, and extends
To FTO transparency conducting layer.
10. a kind of preparation method system of the perovskite solar battery with water-proof function as described in claim 1~9 is any
The standby obtained perovskite solar battery with water-proof function.
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| CN112071994A (en) * | 2020-09-02 | 2020-12-11 | 西北工业大学 | Method for preparing large-size crystal grain perovskite film by blade coating method |
| CN114242902A (en) * | 2021-11-29 | 2022-03-25 | 西北工业大学深圳研究院 | Method for improving air stability of trans-form all-inorganic perovskite solar cell based on ionic liquid |
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| CN114242902A (en) * | 2021-11-29 | 2022-03-25 | 西北工业大学深圳研究院 | Method for improving air stability of trans-form all-inorganic perovskite solar cell based on ionic liquid |
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