CN106910829A - A kind of preparation method of flexible solar battery - Google Patents
A kind of preparation method of flexible solar battery Download PDFInfo
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- CN106910829A CN106910829A CN201710134716.4A CN201710134716A CN106910829A CN 106910829 A CN106910829 A CN 106910829A CN 201710134716 A CN201710134716 A CN 201710134716A CN 106910829 A CN106910829 A CN 106910829A
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Abstract
The invention discloses a kind of preparation method of flexible solar battery, belong to the preparing technical field of solar cell.Technical scheme main points are:New Ti/Ti02/CH3NH3PbI3/P3HT/CNTs structure perovskite flexible solar batteries, Ti electrodes, TiO are followed successively by from substrate upwards2Nanostructured layers, CH3NH3PbI3Type perovskite absorbed layer, polymeric substrate P3HT layers and CNTs transparent conductive film electrode layers, specific preparation process are to prepare TiO in high-purity Ti sheet metals Anodic oxidation2Nanometer layer, then in TiO2Nanometer layer is sequentially prepared other each layers.The present invention prepares TiO using in Ti sheet metals anodizing technology2, substrate Ti sheet metals directly make electrode, while solving TiO2Matched with basal electrode with reference to untight problem, the block solar panel of making has preferable mechanical strength and pliability, and energy conversion efficiency is about 7.1%.
Description
Technical field
The invention belongs to the preparing technical field of solar cell, and in particular to a kind of preparation side of flexible solar battery
Method.
Background technology
As social constantly progressive and expanding economy is to the demand of the energy, energy problem is restriction sustainable economic development
With the major issue of social progress, countries in the world are all in the method for seeking to alleviate even solution energy problem.Exploitation can be again
Raw clean energy resource receives much concern, and is to solve energy problem, realize the key of Sustainable Socioeconomic Development.China pays much attention to can
The research and development of the renewable sources of energy.On March 16th, 2015,23 portions such as the National Development and Reform Commission, the Ministry of Finance, Department of Science and Technology
Committee has held the portion border joint conference for emerging strategic industries development.New Energy Industry and new-energy automobile industry etc. oneself into
For the strategic new industry that China's emphasis is cultivated.State Economic and Trade Commission has formulated " the ten of new and renewable sources of energy industry development
Five " plan, and make and issue《People's Republic of China's Renewable Energy Law》, give priority to solar energy heat utilization, wind-force
Generate electricity, biomass energy efficiently utilize and geothermal energy utilization.Solar energy resources is especially advantageous clean reproducible energy, to it
Develop with solar cell as representative.
Compared to the exploitation of solar cell in the world, the development starting of China than later, but nearly ten years I
State's solar energy energy battery research and development are striking using upper achievement.Representational Ji Jia research institutions in the research of solar energy to reaching
World prostatitis is arrived, Chinese Academy of Sciences's chemistry institute Li Yong boat class groups in 2006 prepare solar cell device energy conversion efficiency and reach
5.4% is reached to 3.18%, 2009 year solar cell energy conversion efficiency of Cao Pu research groups of South China Science & Engineering University preparation, is
International most advanced level at that time, 2011, Cao Pu and Hou Jian brightness group cooperation was in two dimension grips polymer solar material system altogether
Research achieve breakthrough progress, on the basis of polymer P BDTTT introduce instigate fen to grip side chain altogether, obtain device energy
Conversion efficiency is 7.59%, is one of polymer solar battery peak efficiency for reporting at that time, and 2012, the group utilized PEN
Modification ITO electrode prepares reverse solar cell, and energy conversion efficiency breaks through 9%.Solar cell is also evolving progress,
Update, the Ca-Ti ore type solar cell of scientific research personnel's research and development in recent years substantially increases efficiency again, brings solar energy
New development and new record that battery is developed.
With the intelligentized development of electronic product, household electrical appliance and precision instrumentation, and with portable electronic
The increase of equipment and wearable device to power demands, develops bent flexible solar battery device, can improve and use
The flexibility of convenience, arrangement, can be used in the intelligent display of any folding, be beneficial to the revolutionary hair of electronic product
Exhibition.For this respect research it is reported that both at home and abroad have breakthrough team have:Missouri, USA University Engineering Department in 2010
Research team headed by Patrick Pinhero is in a kind of flexible solar battery film of development in laboratory, 85% luminous ray
Absorbed, the available light more than 90% can be captured in theory.In March, 2016 China Science & Technology University Xiong Yujie seminars wound
The property made the Nano silver piece with near-infrared absorption performance and silicon nanowires are integrated, two kinds of different light have been constructed
Volt device, near-infrared region photoelectric transformation efficiency improves 59%.Development high-efficiency soft solar cell very urgently with it is feasible.
The content of the invention
Present invention solves the technical problem that a kind of preparation method of new and effective flexible solar battery is there is provided, effectively
Solve TiO2Matched with basal electrode with reference to untight problem, substrate Ti sheet metals make block solar panel have compared with
Good mechanical strength and pliability.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of preparation side of flexible solar battery
Method, it is characterised in that concretely comprise the following steps:
(1)Substrate Ti/TiO2The preparation of oxidation nanometer layer, ultrasound is clear in being put into acetone after 0.2mm thick Ti sheet metals shearing
15min is washed, then the Ti sheet metals after ultrasonic cleaning are completely cut off into air anneal 3h in 500 DEG C, by the Ti sheet metals after annealing
Contain NH what is prepared4F、H2Anodic oxidation is carried out in the ethylene glycol solution of O and HF, titanium metal plate makees anode, and platinum piece is made cloudy
Pole, the titanium plate after anodic oxidation is calcined 3h in 450 DEG C in atmosphere;
(2)CH3NH3PbI3The preparation of type perovskite absorbed layer, by PbI2And CH3NH3I powder is with mol ratio 1:1 mixed dissolution in
CH is configured in N,N-dimethylformamide3NH3PbI3Precursor liquid, in 70 DEG C with magnetic stirrer to being completely dissolved, by base
Dried after egative film cleaning, take CH3NH3PbI3Precursor liquid spin coating in substrate sheet, then at 115 DEG C of annealing 30min;
(3)P3The preparation of HT hole-conductive layers, by 20mg P3HT obtains P in being dissolved in 2mL dichloro-benzenes3HT precursor liquids, course of dissolution
Need to carry out heating water bath, maintain water temperature at 50 DEG C, with spin-coating film to be used for, by P3HT precursor liquids are spin-coated on substrate sheet
CH3NH3PbI3On type perovskite absorbed layer, then 40min is dried in 70 DEG C in nitrogen atmosphere;
(4)The preparation of CNTs transparent conductive films, CNTs and TNWDIS are blended in aqueous medium, are divided in ultrasonic grinder
Dissipate, then CNTs dispersion liquids are obtained by low speed centrifuge sedimentation, CNTs dispersion liquids are coated in substrate sheet by coating device
P3In HT hole-conductive layers, then drying is obtained flexible solar battery.
Further preferably, step(1)The purity of middle Ti sheet metals is 99.99%.
Further preferably, step(1)In contain NH4F、H2NH in the ethylene glycol solution of O and HF4The weight percentage of F is
0.25%, H2The volumn concentration of O is 1%-2% for the volumn concentration of 2%, HF.
Further preferably, step(2)Middle CH3NH3PbI3The mass concentration of precursor liquid is 40%.
Further preferably, step(3)Middle P3The spin coating revolution of HT precursor liquids is 500rpm.
Further preferably, step(4)Ultrasonic amplitude transformer used by middle CNTs dispersion liquids preparation process is Φ 6, and power output is
60%, the ultrasonic switch time is 3s, and setting total sonication time is 6 × 10min.
The invention has the advantages that:The present invention is prepared for a kind of Ti/TiO2/CH3NH3PbI3/P3HT/CNTs structures
Perovskite flexible solar battery;TiO is prepared using in high-purity Ti sheet metal anodizing technology2Other are sequentially prepared in substrate
Each layer, substrate Ti sheet metals directly make electrode, while solving TiO2Matched with basal electrode with reference to untight problem;Substrate
Ti sheet metals make block solar panel preferable mechanical strength and pliability.
Brief description of the drawings
Fig. 1 is embodiment of the present invention oxidation gained Ti/TiO2The SEM figures on surface;
Fig. 2 is CH prepared by the embodiment of the present invention3NH3PbI3The SEM figures of type perovskite absorbed layer;
Fig. 3 is P prepared by the embodiment of the present invention3HT film atomic force phenograms;
Fig. 4 is the SEM figures of CNTs transparent conductive films prepared by the embodiment of the present invention.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but does not limit in any form of the invention
Content.
Embodiment
Substrate Ti/TiO2The preparation of oxidation nanometer layer
By the thick Ti sheet metals of 0.2mm(Purity is 99.99%)Ultrasonic cleaning in acetone is put into after cutting into 20mm × 20mm
15min, then the Ti sheet metals after ultrasonic cleaning are completely cut off into air anneal 3h in 500 DEG C.Ti sheet metals after annealing are existed
That prepares contains NH4F、H2Anodic oxidation is carried out in the ethylene glycol solution of O and HF, titanium metal plate makees anode, and platinum piece is made cloudy
Pole, NH in electrolyte4The weight percentage of F is 0.25%, H2The volumn concentration of O is that the volumn concentration of 2%, HF is
1%-2%, oxidization time is 5h.Titanium plate after anodic oxidation is calcined 3h, Ti/TiO as shown in Figure 1 in 450 DEG C in atmosphere2Oxidation
The SEM figures on surface.
The CH in substrate3NH3PbI3The preparation of type perovskite absorbed layer
By PbI2And CH3NH3I powder is with mol ratio 1:1 mixed dissolution is in DMF(N,N-dimethylformamide)In be configured to quality
Fraction is about 40% CH3NH3PbI3Precursor liquid, in 70 DEG C with magnetic stirrer to being completely dissolved, after substrate sheet is cleaned
Dry, take appropriate CH3NH3PbI3Precursor aqueous solution spin coating in above-mentioned substrate sheet, then at 115 DEG C of annealing 30min.Such as Fig. 2 institutes
Show CH3NH3PbI3The SEM figures of type perovskite absorbed layer.
P3The preparation of HT hole-conductive layers
By 20mg P3HT is placed in dissolving in 2mL dichloro-benzenes and obtains P3HT precursor liquids, course of dissolution carries out heating water bath, keeps water
Bath temperature is 50 DEG C, with spin-coating film to be employed.By P3HT precursor liquids are spin-coated on the perovskite absorbed layer of above-mentioned substrate sheet,
Precursor liquid is carried out under conditions of spin coating revolution is 500rpm, then 40min is dried in 70 DEG C in nitrogen atmosphere, such as Fig. 3 institutes
Show the thickness the to be formed about P of 200nm3HT film atomic force phenograms.
The preparation of CNTs transparent conductive films
CNTs and TNWDIS are blended in aqueous medium, are disperseed in ultrasonic grinder, then settled by low speed centrifuge
To CNTs dispersion liquids, ultrasonic amplitude transformer used is Φ 6, and power output is 60%, and the ultrasonic switch time is 3s, sets ultrasound total
Time is 6 × 10min.CNTs dispersion liquids are coated in the P of above-mentioned substrate sheet by coating device3In HT hole-conductive layers, then
Drying completes solar battery cell sample making, and the SEM figures of the carbon nanotube conducting layer on surface are grown in as shown in Figure 4.With
Solar cell base experiment instrument is measured to the solar battery cell sample for preparing, and energy conversion efficiency is about 7.1%, institute
The bending pliability of the flexible solar panel solar battery unit of preparation is stronger.
Embodiment above describes general principle of the invention, principal character and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, simply original of the invention is illustrated described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (6)
1. a kind of preparation method of flexible solar battery, it is characterised in that concretely comprise the following steps:
(1)Substrate Ti/TiO2The preparation of oxidation nanometer layer, is cleaned by ultrasonic being put into acetone after 0.2mm thick Ti sheet metals shearing
15min, then the Ti sheet metals after ultrasonic cleaning are completely cut off into air anneal 3h in 500 DEG C, the Ti sheet metals after annealing are existed
That prepares contains NH4F、H2Anodic oxidation is carried out in the ethylene glycol solution of O and HF, titanium metal plate makees anode, and platinum piece is made cloudy
Pole, the titanium plate after anodic oxidation is calcined 3h in 450 DEG C in atmosphere;
(2)CH3NH3PbI3The preparation of type perovskite absorbed layer, by PbI2And CH3NH3I powder is with mol ratio 1:1 mixed dissolution in
CH is configured in N,N-dimethylformamide3NH3PbI3Precursor liquid, in 70 DEG C with magnetic stirrer to being completely dissolved, by base
Dried after egative film cleaning, take CH3NH3PbI3Precursor liquid spin coating in substrate sheet, then at 115 DEG C of annealing 30min;
(3)P3The preparation of HT hole-conductive layers, by 20mg P3HT obtains P in being dissolved in 2mL dichloro-benzenes3HT precursor liquids, course of dissolution
Need to carry out heating water bath, maintain water temperature at 50 DEG C, with spin-coating film to be used for, by P3HT precursor liquids are spin-coated on substrate sheet
CH3NH3PbI3On type perovskite absorbed layer, then 40min is dried in 70 DEG C in nitrogen atmosphere;
(4)The preparation of CNTs transparent conductive films, CNTs and TNWDIS are blended in aqueous medium, are divided in ultrasonic grinder
Dissipate, then CNTs dispersion liquids are obtained by low speed centrifuge sedimentation, CNTs dispersion liquids are coated in substrate sheet by coating device
P3In HT hole-conductive layers, then drying is obtained flexible solar battery.
2. the preparation method of flexible solar battery according to claim 1, it is characterised in that:Step(1)Middle Ti metals
The purity of piece is 99.99%.
3. the preparation method of flexible solar battery according to claim 1, it is characterised in that:Step(1)In contain
NH4F、H2NH in the ethylene glycol solution of O and HF4The weight percentage of F is 0.25%, H2The volumn concentration of O is 2%, HF's
Volumn concentration is 1%-2%.
4. the preparation method of flexible solar battery according to claim 1, it is characterised in that:Step(2)In
CH3NH3PbI3The mass concentration of precursor liquid is 40%.
5. the preparation method of flexible solar battery according to claim 1, it is characterised in that:Step(3)Middle P3HT forerunner
The spin coating revolution of liquid is 500rpm.
6. the preparation method of flexible solar battery according to claim 1, it is characterised in that:Step(4)Middle CNTs points
Ultrasonic amplitude transformer used by dispersion liquid preparation process is Φ 6, and power output is 60%, and the ultrasonic switch time is 3s, when setting ultrasound always
Between be 6 × 10min.
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CN108878653A (en) * | 2018-06-07 | 2018-11-23 | 杭州众能光电科技有限公司 | A kind of flexible perovskite solar battery based on growth in situ hole abstraction, layer |
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CN108878653A (en) * | 2018-06-07 | 2018-11-23 | 杭州众能光电科技有限公司 | A kind of flexible perovskite solar battery based on growth in situ hole abstraction, layer |
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Application publication date: 20170630 |