CN109888112A - A method of efficient stable perovskite solar battery is prepared using cerium oxide - Google Patents
A method of efficient stable perovskite solar battery is prepared using cerium oxide Download PDFInfo
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- CN109888112A CN109888112A CN201910156638.7A CN201910156638A CN109888112A CN 109888112 A CN109888112 A CN 109888112A CN 201910156638 A CN201910156638 A CN 201910156638A CN 109888112 A CN109888112 A CN 109888112A
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- cerium oxide
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- solar battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to perovskite solar battery preparation fields, more particularly to a kind of method for preparing efficient stable perovskite solar battery using cerium oxide；This method main feature is the following steps are included: first is that the preparation of the precursor solution of electron transport material；Second is that there is being mixed with for the electron transport material precursor solution of cerium oxide-doped；Third is that electron transport material precursor solution is in upper FTO spin coating；Fourth is that the assembling of above-mentioned FTO and every technique to battery；It has the advantage that: cerium oxide is introduced into electron transport material, the conduction band minimum of electron transport material is improved, improves the interface stability between perovskite and electron transport material, is more conducive to the extraction and transmission of charge.By the introducing of cerium oxide, efficiency and stability are largely increased, and mainly improve the ultraviolet light stability of battery.
Description
Technical field
The invention belongs to perovskite solar battery preparation fields, prepare efficient stable using cerium oxide more particularly to a kind of
The method of perovskite solar battery.
Background technique
As the important component in perovskite solar battery structure, electron transport material is in charge-extraction and transmission
In play an important role.Common electron transport material has titanium dioxide, zinc oxide and tin oxide.But common electron-transport material
Chemical compatibility between material and perovskite material is general, and level-density parameter is poor, ultraviolet stability difference etc..Perovskite solar-electricity
The photoelectric conversion efficiency (PCE) in pond (PSCs) rapidly rises to 23% or more from 3.8% in 2009, has very big development
Potentiality.The development of efficiency and stability further increased to battery is most important.A large amount of research confirmation, electron transport material
(ETMs) level-density parameter is poor between perovskite and interface charge is compound than more serious etc., has emphatically to PCE and stability
The influence wanted.Therefore, suitable ETM is selected to be of great significance the PSCs for preparing efficient stable.
In common electron transport material, ZnO, TiO2 and SnO2 are had received widespread attention.Wherein, the surface ZnO is aobvious
Alkalinity, so that the proton of MA+ is easy to be captured by ZnO in MAPbI3 under the conditions of slightly higher temperature, so that perovskite
It is destructurized.TiO2 can be catalyzed the decomposition of perovskite under illumination condition.The conduction band minimum of SnO2 is far below perovskite.With
For ZnO, there are poor interface stabilities between ZnO and perovskite interface, and then lead to perovskite during heat treatment
Serious degradation.In addition, the conduction band minimum (CBM) of ZnO is far below perovskite, serious interface obstacles are further defined.Together
When, ZnO shows higher photocatalytic activity as n-type semiconductor under ultraviolet light, and then leads to point of perovskite
Solution.TiO2 and SnO2 also has corresponding defect, especially in terms of ultraviolet light stability.To overcome drawbacks described above, researcher
Utilize the methods of modifying interface passivated surface defect.However, to further increase the PCE and stability of battery, it is also necessary to realize
The electron transport material synergistic effect excellent with the enhancing of perovskite surface chemistry compatibility, level-density parameter, ultraviolet stability.
Summary of the invention
In view of the deficiencies of the prior art and the above problem, efficient stable calcium is prepared using cerium oxide the present invention provides a kind of
The method of titanium ore solar battery, which is characterized in that this method specifically includes:
S1, soluble zinc salt are dissolved in 2-methyl cellosolve, and ethanol amine is added, and dissolve by heating, ZnO electronics is prepared
The precursor solution of transmission material；
S2, cerous acetate is added in the precursor solution of ZnO electron transport material, forms zinc oxide and oxygen by dissolving by heating
Change the electron transport material precursor solution of cerium dopping；
S3, it will be spin-coated on FTO doped with the zinc oxide electron transport material precursor solution of cerium oxide, and at 550 DEG C
Lower annealing 30min obtains fine and close electron transfer layer；
S4, the electron transfer layer containing cerium oxide is successively carried out to the processing of TiCl4 solution, the coating of TiO2 slurry, perovskite
Presoma coating and vacuum metallizing, complete the assembling of battery.
Electron transport material is ZnO, TiO in described S1, S2, S3 and S42Or SnO2, TiO2The forerunner of electron transport material
Solution is dissolved in isopropanol by tetraisopropyl titanate, and heating for dissolving obtains；SnO2The precursor solution of electron transport material passes through
Stannous chloride dihydrate is dissolved in ethyl alcohol, and heating for dissolving obtains.
Preferably, cerous acetate is added to the precursor solution of ZnO electron transport material with the ratio of 3mol% in the S2.
Preferably, the electron transport material heating temperature of the zinc oxide and cerium oxide-doped is 85 DEG C.
In the S3, the zinc oxide electron transport material precursor solution doped with cerium oxide is carried out by spin coating instrument
Coating, the running parameter of spin coating instrument are revolving speed 2800rpm, time 30s.
The invention has the benefit that cerium oxide is introduced into electron transport material, electron transport material is improved most
Small conduction band improves the interface stability between perovskite and electron transport material, is more conducive to the extraction and transmission of charge.
By the introducing of cerium oxide, efficiency and stability are largely increased, and mainly improve the ultraviolet light stability of battery.Oxygen simultaneously
Change cerium incorporation electron transfer layer and also has the advantage that 1) CeOx is one of the most abundant rare-earth oxide on the earth, this
Mean that it has the potentiality of low cost large-scale production.2) chemical stability of CeOx is good, and electron mobility is higher.3)CeOx
There is the ability for converting uv light into visible light, it is advantageous in terms of improving battery ultraviolet light stability.
Detailed description of the invention
Fig. 1 is the energy diagram for preparing solar battery；
Fig. 2 is the Ce elements XPS spectrum figure of doped cerium oxide (powder) in zinc oxide；
Fig. 3 is the Zn-ef ficiency XPS spectrum figure of doped cerium oxide (powder) in zinc oxide；
Fig. 4 is the XRD spectra of doped cerium oxide (powder) in zinc oxide；
Fig. 5 is that the battery efficiency before and after adulterating 3mol%CeOx in ZnO compares figure；
Fig. 6 is under specified moisture, and battery efficiency changes with time figure；
Fig. 7 is under 85 DEG C of heating temperatures, and battery efficiency changes with time figure；
Fig. 8 is under ultraviolet radiator illumination, and battery efficiency changes with time figure；
Specific embodiment
Embodiment 1
In conjunction with the embodiments, the invention will be further described for attached drawing:
The present invention provides a kind of methods for preparing efficient stable perovskite solar battery using cerium oxide, by cerium oxide
It is incorporated into electron transport material (ZnO, TiO2, SnO2 etc.), utilizes the unique 4f electronic structure of rare earth oxide and will be purple
Outer light switchs to the property of visible light, while realizing higher incident photon-to-electron conversion efficiency, improves the stability of battery, especially purple
Outer photostability.
Following steps are by taking ZnO electron transport material as an example.
The preparation of step 1, electron transport material precursor solution: soluble zinc salt such as zinc acetate dihydrate (169mg,
It 0.77mmol) is dissolved in 2.5mL2- methyl cellosolve, 60uL ethanol amine is added, dissolve by heating.
Step 2, cerium oxide-doped zinc oxide precursor solution preparation: by cerous acetate (7.33mg, 0.23mmol) be added
It in above-mentioned zinc oxide precursor liquid solution, is dissolved by heating at 85 DEG C, obtains the precursor solution of cerium oxide-doped zinc oxide.According to figure
Shown in 5 and Fig. 6, the ratio of 3mol%CeOx is adulterated in ZnO and at a temperature of 85 DEG C, battery efficiency is maximum.As shown in Figure 1,
CeOx is directly doped in the precursor solution of zinc oxide, successfully constructs the ETM of ZnO/CeOx.Fig. 2, Fig. 3 and Fig. 4 are respectively
The Ce elements XPS spectrum figure of doped cerium oxide (powder) in zinc oxide, in zinc oxide doped cerium oxide (powder) Zn-ef ficiency XPS spectrum
The XRD spectra of doped cerium oxide (powder) in figure and zinc oxide.It can be obtained from Fig. 2, the valence state of cerium is in the cerium oxide of preparation
Trivalent and tetravalence mixing.It can be obtained from Fig. 3, zinc is contained in solution.It is confirmed from Fig. 4 and is successfully prepared zinc oxide and cerium oxide
Mixed electron transport material.
The preparation of step 3, battery: the preparation of battery is divided into following
S1, by after FTO glass zinc powder and 2mol/L salt acid etch, substrate successively uses acetone, deionized water and ethyl alcohol
Supersound washing.
S2, the precursor solution of cerium oxide-doped zinc oxide is spin-coated on FTO, using spin coating instrument, revolving speed 2800rpm,
Time 30s,
S3, annealing obtains fine and close electron transfer layer to 30min at 550 DEG C.After being cooled to room temperature, compacted zone will be contained
Substrate be put into 75 DEG C of 40mM TiCl4 solution and boil 15 minutes, take out drying.
S4, by the aqueous isopropanol (mass ratio 1:7) of TiO2 slurry (Dyesol DSL 18NR-T) with 5000rpm, 25s
Speed be spun on substrate, anneal 30min at 550 DEG C, to obtain mesoporous layer.
S5,461mg lead iodide and 159mg iodine methylamine are dissolved in 600uLDMF and 70uLDMSO, obtained perovskite
Presoma is spin-coated in substrate with 4000rpm, 25s.
S6, using anti-solvent method, 0.5mL ether is added dropwise in spin coating, anneal at 70 DEG C 1min later, moves back at 100 DEG C
Fiery 2min forms calcium titanium ore bed.
S7, hole mobile material is spin-coated on perovskite with 4000rpm, 25s.Wherein hole mobile material ingredient are as follows:
Spiro-OMeTAD is dissolved in chlorobenzene (72mg/1mL), additive include 17.5uL Li-TFSI/ acetonitrile (520mg/1mL) and
28.8uL TBP。
S8, the gold that 80nm is deposited under 2 × 10-7Torr vacuum condition, complete the assembling of battery.
The introducing of CeOx rises the conduction band minimum of electron transport material by the present invention, to promote perovskite to ETM
Charge injection and transfer.Meanwhile modified ETM film forming is more preferable, further has adjusted the growth of perovskite film.In addition,
Contact between ETM and perovskite is more stable.Based on above-mentioned effect, the PSCs after optimization obtains up to 19.5% PCE.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (5)
1. a kind of method for preparing efficient stable perovskite solar battery using cerium oxide, which is characterized in that this method is specific
Include:
S1, soluble zinc salt are dissolved in 2-methyl cellosolve, and ethanol amine is added, and dissolve by heating, ZnO electron-transport is prepared
The precursor solution of material；
S2, cerous acetate is added in the precursor solution of ZnO electron transport material, forms zinc oxide and cerium oxide by dissolving by heating
The electron transport material precursor solution of doping；
S3, it will be spin-coated on FTO doped with the zinc oxide electron transport material precursor solution of cerium oxide, and moved back at 550 DEG C
Fiery 30min obtains fine and close electron transfer layer；
S4, the electron transfer layer containing cerium oxide is successively carried out to the processing of TiCl4 solution, the coating of TiO2 slurry, perovskite forerunner
Body coating and vacuum metallizing, complete the assembling of battery.
2. a kind of method for preparing efficient stable perovskite solar battery using cerium oxide according to claim 1,
Be characterized in that: electron transport material is ZnO, TiO in described S1, S2, S3 and S42Or SnO2, TiO2The forerunner of electron transport material
Solution is dissolved in isopropanol by tetraisopropyl titanate, and heating for dissolving obtains；SnO2The precursor solution of electron transport material passes through
Stannous chloride dihydrate is dissolved in ethyl alcohol, and heating for dissolving obtains.
3. a kind of method for preparing efficient stable perovskite solar battery using cerium oxide according to claim 1,
Be characterized in that: cerous acetate is added to the precursor solution of ZnO electron transport material with the ratio of 3mol% in the S2.
4. a kind of method for preparing efficient stable perovskite solar battery using cerium oxide according to claim 3,
Be characterized in that: the electron transport material heating temperature of zinc oxide and cerium oxide-doped is 85 DEG C in the S2.
5. a kind of method for preparing efficient stable perovskite solar battery using cerium oxide according to claim 1,
Be characterized in that: the zinc oxide electron transport material precursor solution described in the S3 doped with cerium oxide is carried out by spin coating instrument
Coating, the running parameter of spin coating instrument are revolving speed 2800rpm, time 30s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110400877A (en) * | 2019-06-25 | 2019-11-01 | 兰州大学 | A method of perovskite solar battery is prepared using cerium oxide as mesoporous layer material |
| CN113045211A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof |
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| CN103456888A (en) * | 2013-09-26 | 2013-12-18 | 天津理工大学 | Hybrid solar cell with Cs mingling with ZnO as electron transfer layer |
| CN108447993A (en) * | 2018-03-19 | 2018-08-24 | 吉林大学 | A kind of optical interval layer inversion polymer solar battery |
| US20180315939A1 (en) * | 2017-04-28 | 2018-11-01 | Research & Business Foundation Sungkyunkwan University | Fabrication method of a large area perovskite solar cell |
| CN109301069A (en) * | 2018-10-30 | 2019-02-01 | 深圳清华大学研究院 | Solar cell and preparation method thereof |
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2019
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| CN103456888A (en) * | 2013-09-26 | 2013-12-18 | 天津理工大学 | Hybrid solar cell with Cs mingling with ZnO as electron transfer layer |
| US20180315939A1 (en) * | 2017-04-28 | 2018-11-01 | Research & Business Foundation Sungkyunkwan University | Fabrication method of a large area perovskite solar cell |
| CN108447993A (en) * | 2018-03-19 | 2018-08-24 | 吉林大学 | A kind of optical interval layer inversion polymer solar battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110400877A (en) * | 2019-06-25 | 2019-11-01 | 兰州大学 | A method of perovskite solar battery is prepared using cerium oxide as mesoporous layer material |
| CN110400877B (en) * | 2019-06-25 | 2021-06-08 | 兰州大学 | Method for preparing perovskite solar cell by using cerium oxide as mesoporous layer material |
| CN113045211A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof |
| CN113045211B (en) * | 2019-12-28 | 2022-04-19 | Tcl科技集团股份有限公司 | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof |
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