CN107579134B - Full-inorganic perovskite solar battery and its preparation method and application based on continuous spin coating preparation - Google Patents
Full-inorganic perovskite solar battery and its preparation method and application based on continuous spin coating preparation Download PDFInfo
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Abstract
The present invention provides full-inorganic perovskite solar batteries prepared based on continuous spin coating and its preparation method and application, specifically electron transport material is deposited on FTO or ITO electro-conductive glass, form uniform mesopore film, the then precursor solution of continuous spin coating perovskite material, form the excellent calcium titanium ore bed of crystallinity, back electrode material is finally deposited, the full-inorganic perovskite solar battery being assembled into.By the interface energy level structure of optimization electron transport material and calcium titanium ore bed in the present invention, improve the photoelectric conversion efficiency and stability of battery, at the same have the characteristics that preparation method it is simple, without hole transmission layer, low in cost, room for improvement is big.
Description
Technical field
The invention belongs to new material technology and field of new energy technologies, and in particular to based on continuous spin coating preparation completely without
Machine perovskite solar battery and its preparation method and application.
Background technique
Perovskite solar battery is that the one kind developed in recent years based on solid-state dye sensitized solar battery is had
The novel thin film solar battery of mesoscopic structure.
The working principle of battery are as follows: calcium titanium ore bed absorbs photon, electron transition in its valence band to conduction band, electronics with
Hole flows to the conduction band of electron transfer layer and the valence band of hole transmission layer respectively, to realize the separation of electron-hole pair.Though
The photoelectric conversion efficiency of right current battery has reached commercialized basic demand, but still there are problems that following both sides:
First, due to hole mobile material (such as Spiro-OMeTAD) and traditional perovskite material (such as MAPbI3) use cause electricity
The stability in pond is poor；Second, existing energy level potential barrier causes inside battery current-carrying between carrier blocking layers/calcium titanium ore bed interface
Son is compound serious.Two above problem is unfavorable for the commercial applications of such battery, therefore, develops a kind of stable preparation method
Simply the perovskite solar battery without hole mobile material has important theory significance and practical value.
Summary of the invention
The object of the present invention is to provide the full-inorganic perovskite solar battery prepared based on continuous spin coating and its systems
Preparation Method and application, the present invention can obtain the full-inorganic perovskite solar energy that at low cost, stability is good, photoelectric conversion efficiency is high
Battery allows to promote the functionization of perovskite solar battery, accelerates the industrialization process of perovskite solar battery, tool
There are important practical value and economic value.
For achieving the above object, the present invention is achieved by the following scheme:
The present invention provides the preparation methods of the full-inorganic perovskite solar battery prepared based on continuous spin coating, including with
Lower step:
(1), graphite powder, sodium nitrate and potassium permanganate are dissolved under condition of ice bath according to mass ratio 1 ~ 2:1:5 ~ 8 dense
In sulfuric acid, stirring；
(2), ice bath is removed, the solution is heated to 30 ~ 50 DEG C, after stirring, water and hydrogen peroxide is added until bubble disappears
It loses；
(3), the solution is centrifuged and is cleaned, mixture is dispersed back into water and ultrasound, and it is residual that black is removed after centrifugation
Slag obtains unit for uniform suspension；
(4), suspension is freeze-dried, obtains fluffy solid oxide graphene；
(5), the dimethyl formamide solution of the graphene oxide of 5 ~ 27 mg/mL, ultrasonic disperse, at 150 ~ 200 degree are prepared
Lower heating 8 ~ 12 hours, filters and obtains graphene oxide quantum dot solution；
(6), compound concentration is the isopropyl titanate ethanol solution of 0.1 ~ 1 mol/L, and preparation solubility is 0.05 ~ 0.1 g/mL
TiO2Slurry, compound concentration are the titanium tetrachloride solution of 0.01 ~ 0.05 mol/L；
Compound concentration is 1 ~ 2 mol/L bromination lead solution and concentration is the cesium bromide solution of 0.05 ~ 0.1 mol/L；
(7), by the isopropyl titanate ethanol solution on FTO or ITO electro-conductive glass matrix spin coating at film: forge later
It burns；
(8), by the TiO2Slurry for rotary coating film surface obtained in step (7), is calcined later；
(9), film made from step (8) is immersed in the titanium tetrachloride solution prepared in step (6), at 60 ~ 80 degree
Lower heating, calcining prepares mesoporous titanium dioxide film later；
(10), graphene oxide quantum dot solution prepared by step (5) is spin-coated on titanium deoxid film surface, obtains table
The titanium deoxid film of face modification；
(11), bromination lead solution prepared by step (6) is spin-coated on to the titanium deoxid film surface of step (10) preparation, so
After heat；
(12), cesium bromide solution prepared by step (6) is spin-coated on to the titanium deoxid film surface prepared in step (11),
Then it heats；
(13), the spin coating process repeated in step (12) is multiple, and calcium titanium ore bed is prepared；
(14), carbon pastes are scratched on the calcium titanium ore bed surface, is assembled into battery.
It is further: the solution being centrifuged in the step (3) and is cleaned to supernatant pH 3~4.
It is further: to be freeze-dried suspension 24 ~ 48 hours in the step (4).
Further: titania slurry is prepared by sol-gel self-combustion synthesis in the step (6).
It is further: to be calcined 30 ~ 60 minutes under 450 ~ 550 degree in the step (7).
It is further: to be calcined 30 ~ 60 minutes under 400 ~ 500 degree in the step (8).
It is further: be spin-coated as in the step (10) revolving speed be 2000 revs/min under carry out, the time be 30 seconds.
The present invention also provides full-inorganic perovskite solar batteries made from the preparation method.
Further: the open-circuit voltage of the full-inorganic perovskite solar battery is 1.2~1.4 V, short circuit current 6
~9 mAcm-2, fill factor be 0.6~0.8, photoelectric conversion efficiency is 8~9.5%.
The present invention also provides the full-inorganic perovskite solar batteries as battery component and in power station
Application.
Compared with prior art, it advantages of the present invention and has the technical effect that
1, the present invention makes full use of with gap adjustability, the excellent electron transport ability of graphene oxide quantum dot, passes through
Optimize the interface energy level structure between titanium dioxide and calcium titanium ore bed, multiple spin coating prepares calcium titanium ore bed, accelerates electron-transport mistake
Journey reduces space charge accumulation, reduces the recombination reaction of carrier, hence it is evident that battery performance is improved, by current full-inorganic
The improved efficiency of perovskite solar battery is to 8.5% or so.
2, include the steps that scratching carbon pastes in preparation method of the invention, so perovskite solar energy prepared by the present invention
Battery has the ability of transporting holes without hole transmission layer, carbon electrode.Perovskite solar battery of the invention is without hole transport
Material, preparation cost is lower, while continuous spin-coating method prepares perovskite method is simple, low in cost, room for improvement is big.More
For the ring that it is important that stability of battery is excellent, the full-inorganic perovskite solar battery assembled is 60 ~ 90% in humidity
Follow-on test 30 days under border, battery efficiency is without obvious decaying.
3, the continuous spin-coating method that the present invention uses advantageously reduces in perovskite thin film compared with two-step method traditional at present
CsPb2Br5And Cs4PbBr6The generation of equal non-perovskites phase, to the photoelectric conversion efficiency and stability for improving battery to pass
It is important.
Detailed description of the invention
Fig. 1 is perovskite solar battery prepared by the present invention by the battery effect before and after graphene oxide modifying interface
Rate curve.
Fig. 2 is the stability of full-inorganic perovskite battery prepared by the present invention.
Specific embodiment
The technical scheme of the present invention will be explained in further detail With reference to embodiment.
Embodiment 1
The preparation method of full-inorganic perovskite solar battery of the present invention based on continuous spin coating preparation includes following
Step:
1, natural graphite powder, sodium nitrate and potassium permanganate are dissolved under condition of ice bath according to mass ratio 1 ~ 2:1:5 ~ 8
In the concentrated sulfuric acid, stir 5 ~ 10 minutes；
2, remove ice bath, the solution be heated to 35 DEG C, after stirring 30 minutes, be added 60 ~ 100 mL deionized waters and
The hydrogen peroxide that mass ratio is 3% is until bubble collapse；
3, the solution is centrifuged and is cleaned to supernatant pH 3~4, mixture is dispersed back into water and 20 points of ultrasound
Clock, removal black residue obtains unit for uniform suspension after centrifugation 3 minutes；
4, suspension is freeze-dried 48 hours, obtains fluffy solid oxide graphene；
5, graphene oxide is configured to 9 mg/mL dimethyl formamide solutions (graphene oxide is solute, dimethyl methyl
Amide is solvent), it ultrasonic disperse 30 minutes, is heated 8 hours under 200 degree using solvent-thermal method, filters and obtain graphene oxide
Quantum dot solution；
6, (isopropyl titanate is solute to the isopropyl titanate ethanol solution that compound concentration is 0.5 mol/L, is dissolved in ethyl alcohol
In), the TiO of 0.1 g/mL is prepared by sol-gel self-combustion synthesis2Slurry (TiO2It is dissolved in water), TiO2Particle size is about 20
Nm, compound concentration are the titanium tetrachloride solution of 0.04 mol/L (titanium tetrachloride is dissolved in water)；
Compound concentration is 1 mol/L bromination lead solution (lead bromide is solute, the solution being dissolved in DMF) and concentration is
The cesium bromide solution of 0.07 mol/L (cesium bromide is solute, dissolves solution in methyl alcohol)；
7, by 100 microlitres of isopropyl titanate ethanol solutions on FTO or ITO electro-conductive glass matrix spin coating at film:
Revolving speed is about 7000 revs/min, the time 30 seconds, is calcined 30 minutes under 550 degree later；
8, the TiO for preparing step 62The film surface of slurry for rotary coating in step 7, revolving speed are about 2000 revs/min,
Time is 30 seconds, is calcined 30 minutes under 450 degree later；
9, film made from step 8 is immersed in the titanium tetrachloride solution, is heated 30 minutes under 75 degree, Zhi Hou
450 degree of lower calcinings prepare mesoporous titanium dioxide film；
10, graphene oxide quantum dot solution prepared by step 5 is spin-coated on the titanium deoxid film made from step 9
Surface, revolving speed are 2000 revs/min, and the time is 30 seconds, obtain the titanium deoxid film of surface modification；
11, the bromination lead solution for preparing step 6 is spin-coated on titanium deoxid film surface prepared by step 10, revolving speed
Be 2000 revs/min, the time is 30 seconds, later again 100 degree lower heat 30 minutes；
12, the titanium deoxid film surface that the cesium bromide solution spin coating for preparing step 6 is prepared in a step 11,
Heating 5 minutes under 250 degree；
13, the spin coating process repeated in step 12 is multiple, and calcium titanium ore bed is prepared；
14, carbon pastes are scratched using knife coating in calcium titanium ore bed surface prepared by step 13, is assembled into battery.
As illustrated in fig. 1 and 2, by the above method, obtain that open-circuit voltage is 1.2~1.4 V, short circuit current is 6~9
mA·cm-2, fill factor be 0.6~0.8, photoelectric conversion efficiency is 7.5~9%, is continuously put under conditions of humidity is 60 ~ 90%
30 days battery performances are set without the full-inorganic perovskite solar battery obviously decayed.Full-inorganic perovskite solar energy of the present invention
Battery can be used as battery component and power plant application.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although referring to aforementioned reality
Applying example, invention is explained in detail, for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these are modified or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. the preparation method of the full-inorganic perovskite solar battery based on continuous spin coating preparation, it is characterised in that including following step
It is rapid:
(1), graphite powder, sodium nitrate and potassium permanganate are dissolved in dense sulphur according to mass ratio 1~2:1:5~8 under condition of ice bath
In acid, stirring, obtained solution；
(2), ice bath is removed, the solution is heated to 30~50 DEG C, after stirring, water and hydrogen peroxide is added until bubble collapse；
(3), the solution is centrifuged and is cleaned, mixture is dispersed back into water and ultrasound, and black residue is removed after centrifugation and is obtained
Obtain unit for uniform suspension；
(4), suspension is freeze-dried, obtains fluffy solid oxide graphene；
(5), the dimethyl formamide solution of the graphene oxide of 5~27mg/mL, ultrasonic disperse, under 150~200 degree are prepared
Heating 8~12 hours filters and obtains graphene oxide quantum dot solution；
(6), compound concentration is the isopropyl titanate ethanol solution of 0.1~1mol/L, and preparing solubility is 0.05~0.1g/mL's
TiO2Slurry, compound concentration are the titanium tetrachloride solution of 0.01~0.05mol/L；
The cesium bromide solution that compound concentration is 1~2mol/L bromination lead solution and concentration is 0.05~0.1mol/L；
(7), by the isopropyl titanate ethanol solution on FTO or ITO electro-conductive glass matrix spin coating at film: calcine later；
(8), by the TiO2Slurry for rotary coating film surface obtained in step (7), is calcined later；
(9), film made from step (8) is immersed in the titanium tetrachloride solution prepared in step (6), is added under 60~80 degree
Heat, calcining prepares mesoporous titanium dioxide film later；
(10), graphene oxide quantum dot solution prepared by step (5) is spin-coated on titanium deoxid film surface, obtains surface and repairs
The titanium deoxid film of decorations；
(11), by step (6) prepare bromination lead solution be spin-coated on step (10) preparation titanium deoxid film surface, then plus
Heat；
(12), cesium bromide solution prepared by step (6) is spin-coated on to the titanium deoxid film surface prepared in step (11), then
Heating；
(13), the spin coating process repeated in step (12) is multiple, and calcium titanium ore bed is prepared；
(14), carbon pastes are scratched on the calcium titanium ore bed surface, is assembled into battery.
2. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: the solution is centrifuged in the step (3) and is cleaned to supernatant pH3~4.
3. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: suspension is freeze-dried 24~48 hours in the step (4).
4. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: titania slurry is prepared by sol-gel self-combustion synthesis in the step (6).
5. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: being calcined 30~60 minutes under 450~550 degree in the step (7).
6. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: being calcined 30~60 minutes under 400~500 degree in the step (8).
7. the preparation method of the full-inorganic perovskite solar battery according to claim 1 based on continuous spin coating preparation,
It is characterized by: be spin-coated as in the step (10) revolving speed be 2000 revs/min under carry out, the time be 30 seconds.
8. full-inorganic perovskite solar battery made from the described in any item preparation methods of claim 1~7.
9. full-inorganic perovskite solar battery according to claim 8, it is characterised in that: the full-inorganic perovskite is too
The open-circuit voltage of positive energy battery is 1.2~1.4V, short circuit current is 6~9mAcm-2, fill factor be 0.6~0.8, photoelectricity turn
Changing efficiency is 8~9.5%.
10. full-inorganic perovskite solar battery according to any one of claims 8 is as battery component and for the application in power station.
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| CN108807676A (en) * | 2018-05-16 | 2018-11-13 | 暨南大学 | Wide spectrum based on organic photoactive layers responds inorganic perovskite solar cell and its preparation method and application |
| CN108767122A (en) * | 2018-05-28 | 2018-11-06 | 福州大学 | The preparation and its application of the mesoporous titanium dioxide film material of modified by graphene quantum dot |
| CN108831998B (en) * | 2018-06-08 | 2020-05-19 | 中南大学 | Preparation method of solar cell based on polyelectrolyte inorganic perovskite |
| CN108899421B (en) * | 2018-06-26 | 2022-01-04 | 暨南大学 | All-inorganic perovskite solar cell and preparation method and application thereof |
| CN108963032B (en) * | 2018-06-26 | 2019-12-31 | 暨南大学 | Double-sided inorganic perovskite solar cell and preparation method and application thereof |
| CN109103272A (en) * | 2018-08-02 | 2018-12-28 | 武汉理工大学 | A kind of N-CDs/PVP film, fluorescent solar collector with high-photoelectric transformation efficiency and preparation method thereof |
| CN109802040A (en) * | 2019-01-26 | 2019-05-24 | 中国海洋大学 | Inorganic perovskite solar battery and the preparation method and application thereof based on the compound cavitation layer of poly- 3 hexyl thiophenes/Phthalocyanine Zinc |
| CN112382728A (en) * | 2020-11-13 | 2021-02-19 | 中国科学院大连化学物理研究所 | Battery method for modifying electronic transmission layer of perovskite battery |
| CN113178522B (en) * | 2021-04-20 | 2022-07-26 | 中国海洋大学 | Perovskite solar cell based on halogenated hydroxyl oxide quantum dot interface layer and preparation method |
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| CN104201284B (en) * | 2014-08-29 | 2017-08-25 | 国家纳米科学中心 | A kind of integrated solar cell based on perovskite solar cell and bulk heterojunction solar cell and preparation method thereof |
| CN106981570B (en) * | 2016-01-18 | 2019-11-01 | 北京大学 | A kind of fast preparation method and its application of perovskite thin film |
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