CN104078566A - Method for preparing polymer thin-film solar cell active layer through electrospinning - Google Patents
Method for preparing polymer thin-film solar cell active layer through electrospinning Download PDFInfo
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- CN104078566A CN104078566A CN201410311764.2A CN201410311764A CN104078566A CN 104078566 A CN104078566 A CN 104078566A CN 201410311764 A CN201410311764 A CN 201410311764A CN 104078566 A CN104078566 A CN 104078566A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention relates to a solar cell, and provides a method for preparing a polymer thin-film solar cell active layer through electrospinning, wherein by means of the method, full-spray-printing preparation of a donor material layer, a blending layer and an acceptor material layer can be completely at the same time. The method includes the first step of preparing an electrostatic spinning active layer solution, the second step of conducting lap joint on an electrospinning device and conducting preparation before entering a laboratory, the third step of preparing the donor material layer through electrostatic spraying, the fourth step of preparing a nanometer mesh-shaped porous structure of the blending layer through electrospinning, and the fifth step of preparing the blending layer and the acceptor material layer through electrostatic spraying. When the polymer thin-film solar cell active layer is prepared through the electrospinning technology, experimental equipment is simple, operation is convenient, material applicability is high, a prepared nanofiber membrane is high in specific surface area and is of a nanometer mesh-shaped porous structure, high mechanical strength is achieved, the contact area between a donor and an acceptor is greatly enlarged, and safety and circulating performance of the cell are improved.
Description
Technical field
The present invention relates to solar cell, especially relate to a kind of method that electrospinning is prepared polymer thin-film solar cell active layer.
Background technology
Polymer solar battery, due to its potential price advantage and potential high-energy conversion efficiency (surpassing 8% at present) and the advantage that can make large area flexible device, becomes the study hotspot of international numerous research institution and enterprise in recent years.Polymer solar battery have can in flexible substrate, prepare, the advantage such as lightweight, self discharge is little, memory-less effect, this is traditional not available (Li Gang of mineral crystal silicon solar cell, Zhu Rui, Yang Yang.Polymer solar cells.[J] Nature Photonics, 2012,6 (3): 153-161).
The structure of polymer thin-film solar cell comprises: anode, anodic interface layer, active layer film, cathode interface layer, negative electrode.Wherein, the thickness of active layer and morphosis have material impact to the performance of solar cell, active layer is comprised of donor material layer, blended layer, acceptor material layer conventionally, and blended layer is formed by donor material (conjugated polymer) and acceptor material (fullerene derivate) blend.Due to shorter (the Peumans P of the diffusion length of exciton in conjugated polymer, Yakimow A, Forrest S R.Small molecular weight organic thin-film photodetectors and solar cells.[J] Solar Energy Materials & Solar Cells, 2009,93 (4): 394-412), so donor material and the acceptor material inierpeneirating network structure that need to form nanoscale is realized the collection of the effective separated and electric charge of exciton.When incident illumination is mapped to active layer film, the exciton producing is separated into electronics and hole to the interface of acceptor, and by the continuous inierpeneirating network structure by forming to acceptor material, be transferred to negative electrode and anode generation current respectively, and due to the restriction of exciton diffusion length, need to by the extent control being separated within the scope of 20nm to improve the separative efficiency of exciton.Meanwhile, the thickness of active layer is also the key factor that affects battery performance.Cross thin active layer film lower for the absorptivity of incident light, and easily produce larger leakage current; Blocked up active layer film can cause electric charge to derive, and affects the energy conversion efficiency of battery.Therefore the factor of active layer thickness and form is studied, the active layer film of preparing thickness and form the best is very important.
Electrostatic spinning technique based on electrohydraulic dynamic coupling spray printing is one of common method of preparing nanofiber.Than other technologies of preparing, electrostatic spinning has that equipment is simple, easy to operate, material compatibility is strong, can spray printing solution viscosity advantages of higher (Zheng Gaofeng, Wang Lingyun, Sun Daoheng (2008). " the micro/nano structure direct writing technology based near field electrostatic spinning. " nanometer technology and precision engineering the 6th volume), thereby in recent years, obtained swift and violent development.The power that electrostatic spinning stretches and sprays as spinning solution by applying electrostatic high-pressure, there is deformation and produce taylor cone in electrostatic spinning process viscoelastic solution, and lure that solution penetrates from taylor cone point under the effect of external electric field.Static fluidics can liquid droplets shape or fibrous material, is called electrostatic spray and electrostatic spinning.Wherein, utilize nano/micron particle prepared by electrostatic spray to there is dispersion unicity highly, and the institute of embedding well carrier material; Nano fibrous membrane prepared by electrostatic spinning has high specific area and mesh nanometer loose structure, can form the continuous inierpeneirating network structure of nanoscale.
In the blended layer of active layer film, design the inierpeneirating network structure of mesh nanometer, not only can increase substantially active layer to the contact area of acceptor, and can alleviate in charge and discharge process the destruction that the variation to acceptor material volume causes electrode material structure, keep good electron transfer passage, make polymer thin-film solar cell there is good Capacitance reserve ability and high-multiplying power discharge, improved fail safe and the cycle performance of battery.And document < < Fabrication of ordered bulk heterojunction organic photovoltaic cells using nanopatterning and electrohydrodynamic spray deposition methods > > (Sung-Eun Park, Sehwan Kim, Kangmin Kim.Fabrication of ordered bulk heterojunction organic photovoltaic cells using nanopatterning and electrohydrodynamic spray deposition methods.[J] Nanoscale, 2012, the jagged blended layer structure of utilizing stamping technique to obtain 4:7773-7779), although improved the contact area of active layer to acceptor, but it is limited that battery performance improves, Chinese patent 201010241963.2 has proposed electrostatic spray and has obtained spheric granules embedding institute carrier material, but it is the inierpeneirating network structure that machining is made that blended layer institute carrier material (dividing to body) is appointed, cause donor material and electrostatic spray to obtain spheric granules and contact posterior synechia insufficient strength, and the change in volume of following at battery charge and discharge process, active material (spheric granules) easily comes off from donor material, and structure is destroyed gradually.Chinese patent 200910043369.X proposes a kind of method of preparing micro-nano porous structure polymer electrolyte membrane, but need to pass through spin-coating method, electrostatic spray method, spraying process, should brush method etc. micro-nano technology, complex process, equipment investment is high.
Summary of the invention
The object of the present invention is to provide and can complete the method that a kind of electrospinning prepared by the full spray printing of donor material layer, blended layer, acceptor material layer is prepared polymer thin-film solar cell active layer simultaneously.
The present invention includes following steps:
1) prepare electrostatic spinning active layer solution
By acceptor material solution and the solvent of the donor material solution of active layer, active layer, after stirring, obtain electrostatic spinning active layer solution;
2) before electric spinning device overlap joint and laboratory, prepare
In solution tank, inject electrostatic spinning active layer solution, in liquid feed device, inject feed flow, regulate the feeding rate of liquid feed device, feed speed during regulation and control experiment, collecting board be positioned over shower nozzle under, collecting board ground connection;
3) adopt electric spinning device to prepare donor material layer
Electrospinning solution is the donor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure and makes experiment in electrostatic spray state shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, quilt is pullled tapered, from boring point, ejects drop, and the drop of injection is after collecting board is collected, along with droplet flow and solvent evaporates, at collecting board, form thin film (donor material layer);
4) electrostatic spinning is prepared the mesh nanometer loose structure of blended layer
Experimental solutions is the donor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure and makes experiment in electrostatic spinning, prepare the pattern of fiber shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, pullled tapered, from boring point, eject fiber jet, the fiber jet spraying has the collecting board of the donor material film of active layer to collect in collection after, along with solvent evaporates, at collecting board, form the mesh nanometer fibre membrane with porous structure substrate with good mechanical properties;
5) electrostatic spray is prepared blended layer and acceptor material layer
Electrospinning solution is the acceptor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure to shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, pullled tapered, from boring point, eject drop, after the drop spraying has in collection and collects on the collecting board of donor material mesh nanometer fibre membrane with porous structure of active layer, along with droplet flow and solvent evaporates, nano/micron particle prepared by electrostatic spray technology is the substrate of the micro-nano mesh structural porous structural fibers film of embedding well, the final blended layer mixing mutually to acceptor material that forms, after the mesh nanometer loose structure of the complete embedding donor material of acceptor material nano/micron particle to be prepared, continue electrostatic spray, obtain acceptor material layer, i.e. polymer thin-film solar cell active layer.
In step 1) in, the donor material of described active layer can be conjugated polymer, the optional autohemagglutination 3-of described conjugated polymer hexyl thiophene (P3HT) etc.; The acceptor material of described active layer can be fullerene derivate, and described fullerene derivate can be selected from [6,6]-2-phenyl C
61-2-methyl butyrate (PCBM) etc.; The mass concentration of the donor material solution of described active layer, the acceptor material solution of active layer can be 15mg/ml; Described solvent can adopt chlorobenzene and carrene.
In step 2) in, the feed speed of described liquid feed device can be 200 μ L/h; Described collecting board be positioned over shower nozzle under 50mm place; Described shower nozzle can adopt stainless steel hollow needle, and shower nozzle internal diameter can be 0.21mm.
In step 3) in, the feed speed of described liquid feed device can be 200 μ L/h; Described high pressure can be 15kV; The thickness of described film can be 200nm.
In step 4) in, the feed speed of described liquid feed device can be 200 μ L/h; Described high pressure can be 8kV.
In step 5) in, the feed speed of described liquid feed device can be 200 μ L/h; Described high pressure can be 15kV; The thickness of described blended layer can be 20nm; The thickness of described polymer thin-film solar cell active layer can be 250nm.
The present invention adopts electrostatic spinning technique to prepare polymer thin-film solar cell active layer, experimental facilities is simple, easy to operate, material compatibility strong, the nano fibrous membrane of preparation has high specific area and mesh nanometer loose structure, both there is good mechanical strength, greatly improve again the contact area to acceptor, improved fail safe and the cycle performance of battery.
The present invention uses electrostatic spinning technique preparation to have the mesh nanometer fibre membrane with porous structure substrate of good mechanical properties and has dispersion unicity nano/micron particle highly, and polymer immiscible by two kinds and that have a good ionic conduction ability carries out compound.The mesh nanometer fibre membrane with porous structure substrate of good mechanical properties prepared by employing electrospinning, provides a kind of good mechanical strength that both had, and has again good pick up concurrently, can receive the micro-nano porous structure tunica fibrosa of a large amount of electrolyte; Nano/micron particle prepared by employing electrostatic spray technology is embedding micro-nano porous structure well, and electrostatic spray technology can be prepared the controlled donor material layer of even thickness, acceptor material layer film.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram that electrostatic spray is prepared donor material layer.
Fig. 2 is the apparatus structure schematic diagram that electrostatic spinning is prepared donor material inierpeneirating network structure in blended layer.
Fig. 3 is the apparatus structure schematic diagram that in blended layer, acceptor material is filled inierpeneirating network structure.
Fig. 4 is the donor material layer collected on collecting board and the structural representation of blended layer.
Fig. 5 is the structural representation of the polymer thin-film solar cell active layer prepared of electrospinning.
Fig. 6 is the SEM figure that electrostatic spinning is prepared donor material inierpeneirating network structure in blended layer.
Fig. 7 is the SEM figure of the nano/micron particle of electrostatic spray preparation filling inierpeneirating network structure.
Number in the figure: 1, liquid feed device; 2, solution tank; 3, donor material solution; 4, acceptor material solution; 5, shower nozzle; 6, high voltage source; 7, collecting board; 8, donor material layer; 9, blended layer; 10, acceptor material layer.
Embodiment
Below in conjunction with accompanying drawing, the technical scheme in the invention process is described in detail, these embodiment, only for the present invention is described, limit the scope of application of the present invention and be not used in.
To prepare poly-3-hexyl thiophene (P3HT) and [6,6]-2-phenyl C
61the blend of-2-methyl butyrate (PCBM) is example as active layer, by reference to the accompanying drawings specific works principle of the present invention and operating process is described in detail.
Utilize preparation method of the present invention to prepare the active layer of polymer thin-film solar cell.The process of preparation is as follows:
1. prepare electrostatic spinning active layer solution.
Testing active layer solution P3HT (donor material) used and the mass concentration of PCBM (acceptor material) is 15mg/ml, and solvent is respectively chlorobenzene and carrene.Mixed solution is stirred, obtain spinning active layer solution even, thickness.Solution at room temperature standing 5h is standby.
2. before electric spinning device overlap joint and laboratory, prepare.
As shown in Figures 1 to 3, solution tank 2 is equipped with active layer solution, by regulating the feeding rate of liquid feed device 1, and feed speed during regulation and control experiment (the first feed flow 20min of liquid feed device 1 stablizes feed flow); Collecting board 7 be positioned over shower nozzle 5 under 50mm place, shower nozzle 5 is stainless steel hollow needle, internal diameter 0.21mm.
3. electrostatic spray is prepared donor material layer.
During experiment, electrospinning solution (donor material solution 3) is P3HT, and liquid feed device 1 feed speed is 200 μ L/h, after treating that liquid feed device 1 liquid supply speed is stable, open 6 pairs of shower nozzles of high voltage source 5 in addition the high pressure of 15kV can make experiment in electrostatic spray state.The drop that shower nozzle 5 hangs is under the effect of high voltage electric field, and quilt is pullled tapered, from boring point, ejects fast ultra-fine drop.The drop spraying, after collecting board 7 (ground connection) is collected, along with droplet flow and solvent volatilize fast, forms uniform thin film (being donor material layer 8) at collecting board 7, and by controlling the electrostatic spray time, film thickness is about 200nm.
4. electrostatic spinning is prepared the mesh nanometer loose structure of blended layer.
This step is carried out rapidly after step 3 completes, experimental solutions (donor material solution 3) is P3HT, liquid feed device 1 feed speed is 200 μ L/h, after treating that liquid feed device 1 liquid supply speed is stable, open 6 pairs of shower nozzles of high voltage source 5 in addition the high pressure of 8kV can make experiment in electrostatic spinning, prepare the pattern of fiber.The drop that shower nozzle 5 hangs is under the effect of high voltage electric field, and quilt is pullled tapered, from boring point, ejects fast ultra-fine jet.The fiber spraying is after collecting board 7 (step 3 is collected the collecting board 7 that has P3HT film) is collected, along with solvent volatilizees fast, at collecting board 7, form the mesh nanometer fibre membrane with porous structure substrate with good mechanical properties, be illustrated in figure 6 mesh nanometer loose structure SEM figure.
5. electrostatic spray is prepared blended layer and acceptor material layer.
During experiment, electrospinning solution (acceptor material solution 4) is PCBM, and liquid feed device 1 feed speed is 200 μ L/h, after treating that liquid feed device 1 liquid supply speed is stable, opens the in addition high pressure of 15kV of 6 pairs of shower nozzles of high voltage source 5.The drop that shower nozzle 5 hangs is under the effect of high voltage electric field, and quilt is pullled tapered, from boring point, ejects fast ultra-fine drop, is illustrated in figure 7 the SEM figure of ultra-fine drop particle.The drop spraying is at collecting board 7, be after step 4 is collected and to be collected on the collecting board 7 have P3HT mesh nanometer fibre membrane with porous structure, along with droplet flow and solvent volatilize fast, nano/micron particle prepared by electrostatic spray technology is the substrate of the micro-nano mesh structural porous structural fibers film of embedding well, the final blended layer 9 mixing mutually to acceptor material that forms is about 20nm, as Fig. 4.
After the mesh nanometer loose structure of the complete embedding donor material of acceptor material nano/micron particle to be prepared, continue electrostatic spray a period of time, can obtain the controlled 250nm of being of uniform one deck PCBM film (being acceptor material layer 10, as Fig. 5) thickness.
Claims (10)
1. electrospinning is prepared a method for polymer thin-film solar cell active layer, it is characterized in that comprising the following steps:
1) prepare electrostatic spinning active layer solution
By acceptor material solution and the solvent of the donor material solution of active layer, active layer, after stirring, obtain electrostatic spinning active layer solution;
2) before electric spinning device overlap joint and laboratory, prepare
In solution tank, inject electrostatic spinning active layer solution, in liquid feed device, inject feed flow, regulate the feeding rate of liquid feed device, feed speed during regulation and control experiment, collecting board be positioned over shower nozzle under, collecting board ground connection;
3) adopt electric spinning device to prepare donor material layer
Electrospinning solution is the donor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure and makes experiment in electrostatic spray state shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, quilt is pullled tapered, from boring point, ejects drop, and the drop of injection is after collecting board is collected, along with droplet flow and solvent evaporates, at collecting board, form thin film (donor material layer);
4) electrostatic spinning is prepared the mesh nanometer loose structure of blended layer
Experimental solutions is the donor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure and makes experiment in electrostatic spinning, prepare the pattern of fiber shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, pullled tapered, from boring point, eject fiber jet, the fiber jet spraying has the collecting board of the donor material film of active layer to collect in collection after, along with solvent evaporates, at collecting board, form the mesh nanometer fibre membrane with porous structure substrate with good mechanical properties;
5) electrostatic spray is prepared blended layer and acceptor material layer
Electrospinning solution is the acceptor material solution of active layer, after liquid feed device liquid supply speed is stable, opening high voltage source adds high pressure to shower nozzle, the drop that shower nozzle hangs is under the effect of high voltage electric field, pullled tapered, from boring point, eject drop, after the drop spraying has in collection and collects on the collecting board of donor material mesh nanometer fibre membrane with porous structure of active layer, along with droplet flow and solvent evaporates, nano/micron particle prepared by electrostatic spray technology is the substrate of the micro-nano mesh structural porous structural fibers film of embedding well, the final blended layer mixing mutually to acceptor material that forms, after the mesh nanometer loose structure of the complete embedding donor material of acceptor material nano/micron particle to be prepared, continue electrostatic spray, obtain acceptor material layer, i.e. polymer thin-film solar cell active layer.
2. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 1) in, the donor material of described active layer is conjugated polymer, the optional autohemagglutination 3-of described conjugated polymer hexyl thiophene; The acceptor material of described active layer is fullerene derivate, and described fullerene derivate can be selected from [6,6]-2-phenyl C
61-2-methyl butyrate.
3. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 1) in, the mass concentration of the donor material solution of described active layer, the acceptor material solution of active layer is 15mg/ml; Described solvent can adopt chlorobenzene and carrene.
4. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 1) in, described solvent adopts chlorobenzene and carrene.
5. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 2)～5) in, the feed speed of described liquid feed device is 200 μ L/h.
6. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 2) in, described collecting board be positioned over shower nozzle under 50mm place; Described shower nozzle adopts stainless steel hollow needle, and shower nozzle internal diameter can be 0.21mm.
7. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 3) in, described high pressure is 15kV; The thickness of described film can be 200nm.
8. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 4) in, described high pressure is 8kV.
9. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 5) in, described high pressure is 15kV.
10. a kind of electrospinning is prepared the method for polymer thin-film solar cell active layer as claimed in claim 1, it is characterized in that in step 5) in, the thickness of described blended layer is 20nm; The thickness of described polymer thin-film solar cell active layer can be 250nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966781A (en) * | 2015-05-04 | 2015-10-07 | 青岛大学 | Perovskite nanometer fiber film solar cell and preparation method thereof |
| CN107497644A (en) * | 2017-09-25 | 2017-12-22 | 厦门大学 | The flexible output from driver prepared based on electrostatic spraying method |
| CN107538919A (en) * | 2017-08-28 | 2018-01-05 | 珠海纳金科技有限公司 | Shower nozzle and shower nozzle preparation method |
| CN107632346A (en) * | 2017-09-28 | 2018-01-26 | 厦门大学 | A kind of microsphere resonator manufacture method based on electrohydrodynamic spray printing |
| CN108511609A (en) * | 2018-03-15 | 2018-09-07 | 南京工业大学 | A kind of nanofiber, solar cell and preparation method using the nanofiber |
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| CN102254694A (en) * | 2011-04-20 | 2011-11-23 | 东南大学 | Method for preparing noble metal-modified dye-sensitized solar cell photo-anode based on electrostatic spraying method |
| CN103236502A (en) * | 2013-04-18 | 2013-08-07 | 厦门大学 | Preparation method for activated layer of polymer solar battery |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104966781A (en) * | 2015-05-04 | 2015-10-07 | 青岛大学 | Perovskite nanometer fiber film solar cell and preparation method thereof |
| CN104966781B (en) * | 2015-05-04 | 2018-04-17 | 青岛大学 | A kind of perovskite nanofiber film solar cell and preparation method thereof |
| CN107538919A (en) * | 2017-08-28 | 2018-01-05 | 珠海纳金科技有限公司 | Shower nozzle and shower nozzle preparation method |
| CN107538919B (en) * | 2017-08-28 | 2023-08-29 | 珠海纳金科技有限公司 | Spray head and spray head manufacturing method |
| CN107497644A (en) * | 2017-09-25 | 2017-12-22 | 厦门大学 | The flexible output from driver prepared based on electrostatic spraying method |
| CN107497644B (en) * | 2017-09-25 | 2023-10-20 | 厦门大学 | Flexible self-driver prepared based on electrostatic spraying method |
| CN107632346A (en) * | 2017-09-28 | 2018-01-26 | 厦门大学 | A kind of microsphere resonator manufacture method based on electrohydrodynamic spray printing |
| CN107632346B (en) * | 2017-09-28 | 2020-04-24 | 厦门大学 | Method for manufacturing microsphere resonant cavity based on electrohydrodynamic jet printing |
| CN108511609A (en) * | 2018-03-15 | 2018-09-07 | 南京工业大学 | A kind of nanofiber, solar cell and preparation method using the nanofiber |
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