CN104103759A - Fibrous solar battery based on perovskite type organic lead and iodine compound and preparation method thereof - Google Patents

Fibrous solar battery based on perovskite type organic lead and iodine compound and preparation method thereof Download PDF

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CN104103759A
CN104103759A CN201410339938.6A CN201410339938A CN104103759A CN 104103759 A CN104103759 A CN 104103759A CN 201410339938 A CN201410339938 A CN 201410339938A CN 104103759 A CN104103759 A CN 104103759A
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iodine compound
ore type
solar cell
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carbon nano
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王峰
贾怡
康晓燕
于宇
薄鑫
张伟
李志林
宋夜
吉静
刘景军
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Beijing University of Chemical Technology
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
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Abstract

The invention relates to a fibrous solar battery based on a perovskite type organic lead and iodine compound and a preparation method thereof. The fibrous solar battery based on the perovskite type organic lead and iodine compound sequentially comprises a titanium wire, a titanium dioxide layer, a perovskite type organic lead and iodine compound layer, a conductive polymer layer and a carbon nanotube thin film layer from inside to outside in the radial direction; the perovskite type organic lead and iodide compound serves as a main photoelectric conversion material, and the titanium wire and the carbon nanotube serve as battery electrodes. Compared with traditional silicon-based solar batteries, the fibrous solar battery based on the perovskite type organic lead and iodine compound is low in material costs and simple in preparation method and has potential application prospect.

Description

A kind of fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type and preparation method thereof
Technical field
The present invention relates to solar cell and technology of preparing thereof, relate in particular to a kind of using the organic plumbous iodine compound of Ca-Ti ore type as photoelectric conversion material, using carbon nano-tube film and titanium silk as fibrous solar cell of positive and negative electrode and preparation method thereof, belong to solar cell and technical field of nano material application.
Background technology
In recent years, solar cell industry has obtained larger attention and development.The research report of International Energy Agency < < Technology Roadmaps-Solar Photovoltaic Energy 2010 > > shows, since nearly ten years, solar cell installed capacity is to be greater than every year 40% rate increase.But at present crystal-silicon solar cell mainly be take as main in solar cell market, and share is greater than 85%, although its technical maturity, stable performance, its price is higher.In order to make solar cell walk close to huge numbers of families, promote the well-being of mankind, research and development is low-cost, high efficiency solar cell of new generation, just has more urgent realistic meaning.The consumption that wherein reduces silicon is an effective approach, and as solar cells such as exploitation amorphous silicon, Copper Indium Gallium Selenide, cadmium tellurides, but the development of the solar cell of above material has entered bottleneck.The conversion efficiency of amorphous silicon solar cell, only from 12 % of 1997, is promoted to 13.4 % of 2013; The conversion efficiency of cadmium-Te solar battery also only from 1993 16%, be promoted to 20.4 % of 2013; At industrial battery assembly manufacture view, the < < photovoltaic route map > > of International Energy Agency is also only decided to be 23 %, 12 % and 14 % by the conversion efficiency target of the year two thousand twenty monocrystalline silicon, thin film silicon and cadmium-Te solar battery respectively.
Conversion efficiency than conventional crystal silicon and thin film solar cell nearly ten years increases very micro-, the conversion efficiency of the organic plumbous iodine compound solar cell of Ca-Ti ore type has obtained development by leaps and bounds in nearest 5 years: since people's reported first such as Japanese scholars Kojima A in 2009, by the organic plumbous halide (CH of Ca-Ti ore type 3nH 3pbI 3, CH 3nH 3pbBr 3) sensitization titanium dioxide, obtain the photoelectric conversion efficiency of 3.8 %, to the latest report demonstration of U.S. < < science > > magazine in 2014, the conversion efficiency of Ca-Ti ore type solar cell has been promoted to 19.3 %.
The organic plumbous iodine compound solar cell of Ca-Ti ore type of having delivered in document is plane stacking provisions.Wherein, organic plumbous iodine compound is used for absorbing incident light and produces light induced electron hole pair; In battery one side, electronic conductive layer (being generally titanium dioxide or zinc oxide etc.) is for collecting electronics, and conducts to external circuit by transparent conductive film (as tin indium oxide (ITO) etc.); At battery opposite side, often adopt poly-three hexyl thiophenes (P3HT), 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9 '-spiral shell, two fluorenes (Spiro-OMeTAD), poly-(3,4-Ethylenedioxy Thiophene) conducting polymer such as PEDOT, as hole-conductive layer, is collected hole, finally by metal electrode (being generally gold, silver), conducts to external circuit.Two lateral electrodes and external circuit form closed loop.
Perovskite material not only has excellent photoelectric properties, and its material cost and cheap for manufacturing cost: Ca-Ti ore type absorbed layer material is not containing expensive, rare element, do not need high-purity and harsh crystallinity as crystalline silicon, GaAs, thereby reduced the material cost of battery yet; Material preparation and the battery pack of Ca-Ti ore type solar cell are contained under cryogenic conditions and can complete, and do not need the equipment such as High temperature diffusion and corresponding process procedure, thereby reduced, manufacture the equipment of battery and the cost of equipment operation, are conducive to the extensive use of solar cell.
But at present the Ca-Ti ore type solar cell of bibliographical information is that to take ITO or FTO be Window layer and conductive layer, this has just limited the selection of battery base material.Carbon nano-tube has excellent electricity, optical property, and its carrier mobility can reach 10 5cm 2/ (Vs).By methods such as chemical vapour deposition (CVD), suction filtration, dry-spinning, thermal spraying, rollings, can prepare in batches large area, uniform carbon nano-tube film.The carbon nano-tube film of two dimension has good light transmission and conductivity, is the alternative material of the transparent conductive films such as ITO or FTO, is therefore widely used on photovoltaic, transparent display part.The people such as Rowell M adopt the transparent electrode material (ITO) in single wall carbon nano-tube film substituted polymer (P3HT:PCBM) solar cell, have obtained when using ITO electrode almost suitable photoelectric conversion efficiency; The people such as van de Lagemaat J adopt carbon nano-tube film as the transparent electrode material in polymer (P3HT:PCBM) solar cell, obtain higher conversion efficiency.In addition, carbon nano-tube film and N-shaped crystalline silicon form " carbon nano-tube film-silicon heterojunction solar battery ", have obtained 10% ~ 15% photoelectric conversion efficiency.More than show that carbon nano-tube film is a kind of Window layer of excellence and can collects the material with conduct charges.Therefore,, if be used for the assembling of Ca-Ti ore type solar cell using carbon nano-tube film as transparent conductive film, can expand the range of choice of battery material, the diversity of increase battery composition model.
On the other hand, along with the development of portable intelligent electronic equipment performance, its demand for battery capacity is also increasing, and single dependence lithium battery often can not meet user's requirement.Solar cell can be equipment charge by incident light under the condition without external power supply, is the important supplement of lithium battery.Along with the development of the electronic equipments such as google glasses, intelligent watch, wearable device is also subject to the extensive attention of academia and business circles, correspondingly, can be the exploitation of the solar cell of these electronic device power supplies, also just seems particularly urgent.This type solar cell need have flexibility, be easy to the features such as assembling.Wherein, as ordinary clothing, by fiber, weaving the wearable solar cell of formation is a developing direction.Therefore, as basic composition unit, efficiently, the exploitation of fibrous solar cell cheaply just had very important realistic meaning.The people such as Peng HS be take supporting electrode and the counter electrode of battery that carbon nano-tube filament is colloidal tio 2, by dye molecule, titanium dioxide is carried out to sensitization, between colloidal tio 2 and carbon nanotube counter electrode, add electrolyte, prepare fibrous dye-sensitized cell, and obtained 2.9% photoelectric conversion efficiency.The people such as Zhang S be take titanium silk as substrate, by anode oxidation method, on titanium silk surface, prepare Nano tube array of titanium dioxide, by dye molecule, Nano tube array of titanium dioxide is carried out sensitization and adds electrolyte, take carbon nano-tube film as to electrode, prepare fibrous dye-sensitized cell, and obtained 2.6% photoelectric conversion efficiency.Above two kinds of fiber solar cells all belong to dye-sensitized solar cells category, with dye molecule, titanium dioxide are carried out to sensitization therein, by electrolyte transmission charge.Since the reason such as volatile of electrolyte, the problem that battery existence and stability is poor.Therefore, the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type, utilizes the advantage of Nano tube array of titanium dioxide and carbon nano-tube film layer, compares with above-mentioned battery, has cheaply, and synthesis technique is simple, transformation efficiency high.
Summary of the invention
The object of this invention is to provide a kind of fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type and preparation method thereof, utilize the electrical and optical properties of the organic plumbous iodine compound of Ca-Ti ore type, with a kind of technique method simple, with low cost, prepare fiber solar cell, for the application of the organic plumbous iodine compound of Ca-Ti ore type in fibre cell field lays the foundation.
A kind of fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type of the present invention, in its radial direction, comprise successively from the inside to the outside titanium silk, titanium dioxide layer, the organic plumbous iodine compound layer of Ca-Ti ore type, conductive polymer coating and nano-tube film layer, it is fibrous that battery is, wherein the organic plumbous iodine compound of Ca-Ti ore type is as main photoelectric conversion material, and titanium silk and carbon nano-tube are battery electrode.
The present invention also provides the preparation method of the above-mentioned fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type, and concrete preparation technology comprises the steps:
(1) titanium silk is carried out to ultrasonic processing with watery hydrochloric acid and acetone successively;
(2) preparation NH 4f, H 2the ethylene glycol solution of O and HF, puts into this solution by the titanium silk after processing, and utilizes galvanostat to carry out anodic oxidation, after reaction in air ambient with 300 ~ 500 ℃ of calcinings, insulation 1 ~ 5h, obtains titanium dioxide layer;
(3) product obtaining in (2) is put into PbI successively 2organic solution and CH 3nH 3in I organic solution, soak, in protective gas atmosphere, dry, obtain the organic plumbous iodine compound layer of Ca-Ti ore type;
(4) product (3) being obtained is put into the organic solution of conducting polymer and is soaked 5s ~ 10min, in protective gas atmosphere, dries, and obtains conductive polymer coating;
(5) by the coated one deck carbon nano-tube film of the product obtaining in (4), make carbon nano-tube film and conductive polymer coating close contact, as battery electrode, and draw with wire.
In a preferred embodiment of the present invention, in the solution of above-mentioned steps (2), NH 4f content is 0.1 ~ 0.5wt%, H 2content 1 ~ 5vol% of O, the content of HF is 0.5 ~ 5vol%.
In a preferred embodiment of the present invention, in the anode oxidation process of above-mentioned steps (2), voltage control is at 10 ~ 100V, time 10s ~ 60min.
In a preferred embodiment of the present invention, in above-mentioned steps (3), PbI 2solvent be DMF, its concentration is 1 ~ 10M, soak time is 1 ~ 60s; CH 3nH 3the solvent of I is gamma-butyrolacton or isopropyl alcohol, and its concentration is 10 ~ 100mg/mL, and soak time is 1 ~ 60min.
In a preferred embodiment of the present invention, in above-mentioned steps (4), the solvent of conducting polymer is chlorobenzene or 1,2-dichloro-benzenes, and its concentration is 10 ~ 100mg/mL.
In a preferred embodiment of the present invention, the bake out temperature of step (3) and step (4) is 20 ~ 100 ℃, and drying time is 10-100min.
In a preferred embodiment of the present invention, described titanium filament diameter is 0.01 ~ 2 mm.
In a preferred embodiment of the present invention, the organic plumbous iodine compound layer thickness of described Ca-Ti ore type is 50 nm ~ 2 μ m.
In a preferred embodiment of the present invention, described conductive polymer coating comprises poly-three hexyl thiophenes (P3HT), 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9 '-spiral shell, two fluorenes (Spiro-OMeTAD) or poly-(3,4-Ethylenedioxy Thiophene) are (PEDOT).
In a preferred embodiment of the present invention, described carbon nano-tube is single wall carbon nano-tube film, double-walled carbon nano-tube film or multi-wall carbon nano-tube film, and its thickness is 50-200 nm.
The organic plumbous iodine compound that the present invention uses is photoelectric conversion material, and, there is very large absorption region its energy gap 1.5eV left and right to visible ray, is therefore conducive to improve the conversion efficiency of solar cell; Titanium silk and the carbon nano-tube film electrode material as solar cell is usingd in the present invention, the preparation of battery material and be assembled under cryogenic conditions and can complete, do not use the material that silicon etc. involves great expense, so with respect to traditional silica-based solar cell, preparation technology is simple, and manufacturing cost is extremely cheap.The current prepared fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type, its open circuit voltage 0.589V, short circuit current 12.11mA/cm 2, photoelectric conversion efficiency reaches 3.36%, has potential application prospect.
Accompanying drawing explanation
The structural representation of the fibrous solar cell of Fig. 1 based on the organic plumbous iodine compound of Ca-Ti ore type;
Wherein, 1 is titanium silk, and 2 is titanium dioxide layer, and 3 is the organic plumbous iodine compound layer of Ca-Ti ore type, and 4 is conductive polymer coating, and 5 is carbon nano-tube film layer;
In Fig. 2 embodiment 3, the stereoscan photograph of enveloped carbon nanometer tube film not.The organic plumbous iodine compound layer of Ca-Ti ore type from top to bottom successively, titanium dioxide layer, the substrate of titanium silk;
In Fig. 3 embodiment 3, the stereoscan photograph that carbon nano-tube film is battery electrode;
In Fig. 4 embodiment 3, the J-V curve of battery device illumination state.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
Using single wall carbon nano-tube film as battery electrode:
(1) titanium silk is used to the ultrasonic processing of watery hydrochloric acid, the acetone 15min of 1M successively.
(2) preparation NH 4f content is 0.2wt%, H 2the content 2vol% of O, the ethylene glycol solution that the content of HF is 1vol%.Titanium silk after processing being placed in solution, utilizing galvanostat, is under 10V, to carry out anodic oxidation reactions 20min at voltage.500 ℃ of calcinings in air ambient after reaction, insulation 3h, obtains titanium dioxide layer.
(3) product obtaining in (2) is being contained to 1M PbI successively 2dMF solution in soak 20s, containing 10mg/mL CH 3nH 3in the aqueous isopropanol of I, soak 10min, in nitrogen atmosphere, dry 30min for 70 ℃.Form the organic plumbous iodine compound layer of Ca-Ti ore type.
(4) product obtaining in (3) is being contained to 10mg/mL 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,1 of 9 '-spiral shell, two fluorenes (Spiro-OMeTAD), in 2-dichlorobenzene solution, soak 10s, in nitrogen atmosphere, dry 30min, obtain conductive polymer coating for 70 ℃.
(5) by the coated one deck single wall carbon nano-tube film of the product obtaining in (4), make carbon nano-tube film and conductive polymer coating close contact, as battery electrode, and draw with wire.
Embodiment 2
Using multi-wall carbon nano-tube film as battery electrode:
(1) titanium silk is used to the ultrasonic processing of watery hydrochloric acid, the acetone 15min of 1M successively.
(2) preparation NH 4f content is 0.2wt%, H 2the content 2vol% of O, the ethylene glycol solution that the content of HF is 1vol%.Titanium silk after processing being placed in solution, utilizing galvanostat, is under 10V, to carry out anodic oxidation reactions 20min at voltage.500 ℃ of calcinings in air ambient after reaction, insulation 3h, obtains titanium dioxide layer.
(3) product (2) being obtained is containing 1M PbI successively 2dMF solution in soak 20s, containing 10mg/mL CH 3nH 3in the aqueous isopropanol of I, soak 10min, in nitrogen atmosphere, dry 30min for 70 ℃.Form the organic plumbous iodine compound layer of Ca-Ti ore type.
(4) product (3) being obtained is containing 10mg/mL 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,1 of 9 '-spiral shell, two fluorenes (Spiro-OMeTAD), in 2-dichlorobenzene solution, soak 10s, in nitrogen atmosphere, dry 30min, obtain conductive polymer coating for 70 ℃.
(5) by the coated one deck multi-wall carbon nano-tube film of the product obtaining in (4), make carbon nano-tube film and conductive polymer coating close contact, as battery electrode, and draw with wire.
Embodiment 3
To gather three hexyl thiophenes (P3HT), prepare conductive polymer coating:
(1) titanium silk is used to the ultrasonic processing of watery hydrochloric acid, the acetone 15min of 1M successively.
(2) preparation NH 4f content is 0.2wt%, H 2the content 2vol% of O, the ethylene glycol solution that the content of HF is 1vol%.Titanium silk after processing being placed in solution, utilizing galvanostat, is under 10V, to carry out anodic oxidation reactions 20min at voltage.After reaction, be placed on 500 ℃ of calcinings in air ambient, insulation 3h, obtains titanium dioxide layer.
(3) product obtaining in (2) is being contained to 1M PbI successively 2dMF solution in soak 20s, containing 10mg/mL CH 3nH 3in the aqueous isopropanol of I, soak 10min, in nitrogen atmosphere, dry 30min for 70 ℃.Form the organic plumbous iodine compound layer of Ca-Ti ore type.
(4) by the product obtaining in (3) containing 1 of poly-three hexyl thiophenes (P3HT) of 10mg/mL, in 2-dichlorobenzene solution, soak 10s, in nitrogen atmosphere, dry 30min, obtain conductive polymer coating for 70 ℃.
(5) by the coated one deck multi-wall carbon nano-tube film of the product obtaining in (4), make carbon nano-tube film and conductive polymer coating close contact, as battery electrode, and draw with wire.
Pattern during enveloped carbon nanometer tube film not as can be seen from Figure 2.The organic plumbous iodine compound layer of Ca-Ti ore type from top to bottom successively, titanium dioxide layer, the substrate of titanium silk.
Carbon nano-tube film be battery electrode stereoscan photograph as shown in Figure 3.
The J-V curve of the battery device illumination state of test as shown in Figure 4.Wherein open circuit voltage is 0.589V, and short-circuit current density is 12.11mAcm -2, fill factor, curve factor is 0.47, photoelectric conversion efficiency is 3.36%.
Above embodiment shows and has described principal character and the basic preparation method of solar cell of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; the above is preferred embodiment of the present invention; rather than limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.

Claims (9)

1. the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type, it is characterized in that, its radial direction, comprise successively from the inside to the outside titanium silk (1), titanium dioxide layer (2), the organic plumbous iodine compound layer of Ca-Ti ore type (3), conductive polymer coating (4) and carbon nano-tube film layer (5), it is fibrous that battery is, wherein the organic plumbous iodine compound of Ca-Ti ore type is as main photoelectric conversion material, and titanium silk and carbon nano-tube are battery electrode.
2. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type claimed in claim 1, it is characterized in that the preparation method of this battery comprises the steps:
(1) titanium silk is carried out to ultrasonic processing with watery hydrochloric acid and acetone successively;
(2) preparation NH 4f, H 2the ethylene glycol solution of O and HF, puts into this solution by the titanium silk after processing, and utilizes galvanostat to carry out anodic oxidation, after reaction in air ambient with 300 ~ 500 ℃ of calcinings, insulation 1 ~ 5h, obtains titanium dioxide layer;
(3) product obtaining in (2) is put into PbI successively 2organic solution and CH 3nH 3in I organic solution, soak, in protective gas atmosphere, dry, obtain the organic plumbous iodine compound layer of Ca-Ti ore type;
(4) product (3) being obtained is put into the organic solution of conducting polymer and is soaked 5s ~ 10min, in protective gas atmosphere, dries, and obtains conductive polymer coating;
(5) by the coated one deck carbon nano-tube film of the product obtaining in (4), make carbon nano-tube film and conductive polymer coating close contact, as battery electrode, and draw with wire.
3. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type claimed in claim 2, it is characterized in that the NH in ethylene glycol solution 4f content is 0.1 ~ 0.5wt%, H 2content 1 ~ 5vol% of O, the content of HF is 0.5 ~ 5 vol%.
4. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type claimed in claim 2, it is characterized in that, in the anode oxidation process of step (2), voltage control is at 10 ~ 100V, time 10s ~ 60min.
5. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type claimed in claim 2, it is characterized in that PbI 2solvent be DMF, its concentration is 1 ~ 10M, soak time is 1 ~ 60s; CH 3nH 3the solvent of I is gamma-butyrolacton or isopropyl alcohol, and its concentration is 10 ~ 100mg/mL, and soak time is 1 ~ 60min; The solvent of conducting polymer is chlorobenzene or 1,2-dichloro-benzenes, and its concentration is 10 ~ 100mg/mL; Bake out temperature is 20 ~ 100 ℃, and drying time is 10-100min.
6. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type described in claim 1 or 2, it is characterized in that, described titanium filament diameter is 0.01 ~ 2 mm.
7. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type described in claim 1 or 2, it is characterized in that, the organic plumbous iodine compound layer thickness of described Ca-Ti ore type is 50 nm ~ 2 μ m.
8. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type described in claim 1 or 2, it is characterized in that, described conductive polymer coating comprises poly-three hexyl thiophenes, 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9 '-spiral shell, two fluorenes or poly-(3,4-Ethylenedioxy Thiophene).
9. according to the fibrous solar cell based on the organic plumbous iodine compound of Ca-Ti ore type described in claim 1 or 2, it is characterized in that, described carbon nano-tube is single wall carbon nano-tube film, double-walled carbon nano-tube film or multi-wall carbon nano-tube film, and its thickness is 50-200 nm.
CN201410339938.6A 2014-07-17 2014-07-17 Fibrous solar battery based on perovskite type organic lead and iodine compound and preparation method thereof Pending CN104103759A (en)

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CN104900808A (en) * 2015-04-23 2015-09-09 中国科学院宁波材料技术与工程研究所 Method for processing perovskite crystal film by solvent and application of method
CN105140403A (en) * 2015-10-13 2015-12-09 南京大学昆山创新研究院 Planar structure perovskite solar cell with uniform dense layer and preparation method thereof
CN105655447A (en) * 2016-04-01 2016-06-08 合肥工业大学 Large-area preparation method of perovskite films suitable for various substrate shapes
CN106910829A (en) * 2017-03-08 2017-06-30 新乡学院 A kind of preparation method of flexible solar battery
CN107195786A (en) * 2017-06-02 2017-09-22 新乡学院 A kind of preparation method of TiOx nano fiber based perovskite flexible solar battery
CN108878655A (en) * 2018-06-22 2018-11-23 北京协同创新研究院 A kind of fibrous type perovskite solar battery and the preparation method and application thereof
CN110212094A (en) * 2019-05-10 2019-09-06 深圳大学 A kind of preparation method of the flexible photoelectric device of novel perovskite material
CN113023841A (en) * 2021-03-17 2021-06-25 宜兴禹博治环保科技有限公司 Method for electrochemically treating and strengthening coking wastewater

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* Cited by examiner, † Cited by third party
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CN104900808A (en) * 2015-04-23 2015-09-09 中国科学院宁波材料技术与工程研究所 Method for processing perovskite crystal film by solvent and application of method
CN105140403A (en) * 2015-10-13 2015-12-09 南京大学昆山创新研究院 Planar structure perovskite solar cell with uniform dense layer and preparation method thereof
CN105655447A (en) * 2016-04-01 2016-06-08 合肥工业大学 Large-area preparation method of perovskite films suitable for various substrate shapes
CN105655447B (en) * 2016-04-01 2017-02-08 合肥工业大学 Large-area preparation method of perovskite films suitable for various substrate shapes
CN106910829A (en) * 2017-03-08 2017-06-30 新乡学院 A kind of preparation method of flexible solar battery
CN107195786A (en) * 2017-06-02 2017-09-22 新乡学院 A kind of preparation method of TiOx nano fiber based perovskite flexible solar battery
CN108878655A (en) * 2018-06-22 2018-11-23 北京协同创新研究院 A kind of fibrous type perovskite solar battery and the preparation method and application thereof
CN110212094A (en) * 2019-05-10 2019-09-06 深圳大学 A kind of preparation method of the flexible photoelectric device of novel perovskite material
CN113023841A (en) * 2021-03-17 2021-06-25 宜兴禹博治环保科技有限公司 Method for electrochemically treating and strengthening coking wastewater
CN113023841B (en) * 2021-03-17 2023-08-15 宜兴禹博治环保科技有限公司 Method for electrochemically treating intensified coking wastewater

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