CN103897391B - Photo-curing polyimide membrane for thin-film solar cell and preparation method of photo-curing polyimide membrane - Google Patents
Photo-curing polyimide membrane for thin-film solar cell and preparation method of photo-curing polyimide membrane Download PDFInfo
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- CN103897391B CN103897391B CN201210587629.1A CN201210587629A CN103897391B CN 103897391 B CN103897391 B CN 103897391B CN 201210587629 A CN201210587629 A CN 201210587629A CN 103897391 B CN103897391 B CN 103897391B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a photo-curing polyimide membrane for a thin-film solar cell and a preparation method of the photo-curing polyimide membrane. The photo-curing polyimide membrane comprises the following components in parts by weight: 100 parts of polyimide, 0.0001-0.1 part of nano aluminite powder, 0.5-1.25 parts of light curing agent, 0.1-0.2 part of antioxidant, 0.1-0.2 part of ultraviolet absorbent and 0.1-0.2 part of amine light stabilizer. The method comprises the following steps: blending the polyimide, the nano aluminite powder, the light curing agent, the antioxidant, the hindered amine light stabilizer and the like by adopting screw-type blending and extruding equipment; extruding and introducing into a casting mold head after filtrating; and carrying out the procedures of cooling, drafting, rolling and the like, so as to obtain the photo-curing polyimide membrane for the thin-film solar cell. The fabricated photo-curing polyimide membrane is attached to the illuminated surface of the thin-film solar cell or an upper packaging film of the solar cell, so that the flexibility or the generating efficiency of the thin-film solar cell is directly improved.
Description
Technical field
The present invention relates to a kind of flexible or thin-film solar cells photocurable polyimide film and preparation method thereof, passes through
The surface of flexibility or thin-film solar cells incidence surface is encapsulated in using the film, flexible or thin-film solar cells are directly improved
Efficiency.
Background technology
In the middle of the effectively utilizes project of solar energy：Solar photovoltaic utilization is research with fastest developing speed in the last few years, most active
Field.The making of general solaode is mainly based on semi-conducting material, is absorbed using photoelectric material and occur after luminous energy
Opto-electronic conversion reaction generates electricity.According to the difference of material therefor, solaode can be divided into：1st, silicon solar cell；2nd, with inorganic
Solaode of the salt such as multi-element compounds such as GaAs III-V compound, cadmium sulfide, CIS for material；3rd, it is high with function
Solaode prepared by molecular material；4th, nano-crystalline solar battery etc..
Prior art work efficiency highest is the product with Group III-V semiconductor inorganic material as raw material.For example:
The quantum well of the single junction type of GaAs/germanium falls into crystal structure, and its photoelectric transformation efficiency is reachable>18 % ；And multiple junction quantum well
The solar cell of sunken crystal structure, for example:InGaP/GaAs/germanium, its photoelectric transformation efficiency may be up to>30 %.At present should
With most wide, based on silicon：Including non-crystalline silicon, about 9 % of photoelectric transformation efficiency；Polysilicon, about 14 % of photoelectric transformation efficiency；Monocrystalline
Silicon, about 17 % of photoelectric transformation efficiency.Although in price, VI races elements Si is more cheap than Group III-V semiconductor GaAs, its system
The price made, it is compared with macromolecule organic solar batteries or expensive many；And in application, the anxiety of light weight again crack-free
Overall plasticization organic solar batteries can via printing processing realize, in addition to price reduction, be more suitable for portable electronic product
Demand, and indoors or the cloudy day normally can use（This is that siliceous solaode is beyond one's reach）So that its reality
More lifted using range with property and market.
Solaode is a key technology, can advance the production of energy more cleaned.But the cost of solaode
Problem, reduces the economic competitiveness of heliotechnics.To overcome this problem, thin-film solar cells are to be widely used at present
Technology, the usage amount of expensive semi-conducting material can be reduced in a large number, but the absorbing amount of thin-film solar cells is relatively low, performance
Less than traditional solaode.
Thin-film solar module is by glass substrate, metal level, transparency conducting layer, electrical function box, glueing material, partly leads
What body layer etc. was constituted.Organic-inorganic composite solaode is based on organic conjugate polymer-inorganic nano crystal composite material
The solaode of system, because having high-molecular organic material good film-forming property simultaneously, level structure and band gap can easily be accommodated, Ke Yitong
Overly moist method prepares low cost, large area, flexible solar battery device and inorganic nano-crystal material high stability, high migration
Rate, the advantages of can construct ordered nano-structure, and becomes the study hotspot of area of solar cell in recent years.Metal nanoparticle
Solaode can preferably be entered with direct light, prevent light from escaping.In traditional " thick film " solaode, nanoparticle
There is no any effect, because all of light absorption is all by this film, this just relies on its thickness.However, for thin film
For, nanoparticle can just play great role.Their scattering increased the light stop time in the film, make overall suction
The light of receipts reaches a kind of level, and can match in excellence or beauty traditional solaode.
Aluminum can focus light into solaode with Nano silver grain in the frequency spectrum of visible part well.But
It is that optical resonance also results in nanoparticle absorbing light, this means that the efficiency of solaode can be relatively low.Nano silver grain
Resonance is just in solaode key absorption spectrum part, so the absorption of light is appreciable.Aluminum nanoparticles are altogether
Shake beyond solaode key spectra part.Loss to energy is less, additionally, aluminum particulate is easy to passivation, although meeting
Change shapes and sizes, nanoparticle attribute change very little after passivation.Nanoparticle has rough surface, scattering light meeting
Wide spectrum wave-length coverage is entered more.This can bring bigger absorption, so as to improve the whole efficiency of battery.
Due to High-tech Material aromatic series polypyromelliticimide（PI）Resin have insoluble, infusibility, highest level it is resistance to
Hot, tolerance to cold, non-oxidizability, radiation resistance, chemical resistance, good mechanically and electrically characteristic, are widely used in many
Field.Particularly optically transparent PI films have special applications in some fields, such as flexible solar anti-radiation protection material, too
Light in positive energy cell substrates material, flexible transparent conducting film baseplate material, the aligning film material of liquid crystal display, communication field
Optics half-wave plate of waveguide material and planar lightwave circuit etc..
Due to there is height conjugated structure and/or intermolecular formation charge transfer complex in most of aromatic series PI（CT
C）Make which have strong absorption in visible region, in light yellow or dark-brown, limit its application in optical field.By
There is higher softening temperature and limited solubility in which, therefore there are processing difficulties.The processing of PI is with poly- mostly
Amic acid solution form is carried out, and after cast film forming, Jing hot-imides obtain PI thin film.This method is simple, but exists
Some intrinsic shortcomings, the storage period of such as polyamic acid are shorter, due to producing volatile byproducts during imidizate（Such as
Water）And it is also easy to produce defect.In order to overcome these defects, people to do many researchs with regard to solubility and machinability PI.Can dissolve
Property allow to process with PI forms, it is to avoid some problems that processing polyamic acid is brought, this is for microelectronics and optical field
Using being particularly important.
From on Molecular Design increase PI the transparency principle be to avoid or reduces conjugate unit, reduction intramolecular or
Intermolecular load transfer effect, common method have：（1）Introduce fluoro-containing group；（2）Introduce the larger substituent group of volume, such as cast knot
Structure and other big side bases；（3）The 2 of biphenyl, 2 '-position introduces substituent group to produce non-co-planar structure, and destruction is in a big way
Conjugation；（4）Fat is introduced, especially alicyclic structure unit；（5）Using the monomer that can make backbone twist, such as 3,4 '-and 3,
3 '-dianhydride, diamidogen that meta replaces etc..
Improving the deliquescent methods of PI has two kinds：A kind of is to introduce the structure to solvent with affinity；Another kind is to beat
The order and symmetry of random macromolecular chain, the interaction for weakening molecule interchain make the structure of polymer become " loose ", have
Body method has：（1）Introduce fluorine-containing, silicon, the group of phosphorus or hydroxyl；（2）Introduce " circle " shape structure；（3）Introduce side base；（4）Make big
Strand bends；（5）Introduce lipid structure etc..
Polyimide film sheet, as the wide variety of encapsulation film of solaode, is to adapt to above industrial requirement, we
The modified photocurable polyimide film of nanometer aluminium powder is invented.The film can be both used at the backlight of thin-film solar cells,
Thin-film solar cells can also be used in enters light film surface, while the centre of thin-film solar cells can also be used in
Layer, improves the efficiency of light absorption of solaode.Improve the generating efficiency of solaode.The content of the invention
It is an object of the invention to provide a kind of flexible or thin-film solar cells photocurable polyimide film and its preparation
Method, is encapsulated in the surface of flexibility or thin-film solar cells incidence surface by using the film, directly improves flexible or thin film too
The efficiency of positive energy battery.And have encapsulated flexible or thin-film solar cells there is self-cleaning effect.
For achieving the above object, the technical solution used in the present invention is as follows：
The thin-film solar cells photocurable polyimide film of the present invention, mainly by the following component system of following weight parts
Into：Polyimides 100；Nanometer aluminium powder 0.0001-0.1；Light curing agent 0.5 ~ 1.25；Antioxidant 0.1 ~ 0.2；Ultraviolet absorber
0.1~0.2；Amine light stabilizer 0.1 ~ 0.2.
Described polyimide resin is that Jing introduces fluorine-containing, silicon, the group of phosphorus or hydroxyl or introduces the larger replacement of volume
Base（Such as cast structural and other big side bases or the 2 of biphenyl, 2 '-position introduces substituent group to produce non-co-planar structure）It is broken
Bad large range of conjugation bends macromolecular chain, introduces fat, and especially alicyclic structure unit or employing can make main chain curved
Bent monomer（Such as 3,4 '-and 3,3 '-dianhydride, the diamidogen that meta replaces）Deng modified polyimide resin.
Gather disclosed in such as Chinese patent CN102504255A, CN1970603A, CN102558556A, CN1018183B
Imide resin；Or document：1. face is apt to silver etc., the conjunction of new diamidogen containing pyridine ring and its solvable transparent fluorinated polyimide
Into with sign, synthetic technology and apply the 03rd phase 5-12 in 2010,2. He Man etc., fluorinated polyimide containing benzothiazole prepare and
Nonlinear optical property, Acta PhySico-Chimica Sinica, polyimide resin disclosed in 2010,26,3073-3079.
Amine light stabilizer is double（1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls）Last of the ten Heavenly stems diester or（2,2,6,6- tetra-
Methyl -4- piperidyls）Sebacate, poly-succinic（- 1 piperidinyl-acetate of 4 hydroxyl -2,2,6,6- tetramethyls）In one kind or several
The mixing planted.
Described light curing agent is aromatic carbonyl, preferably phenyl ketone based compound, such as dibenzoyl, hexichol
Ketone, Benzoinum and its ether derivative.
Antioxidant is three（2,4- di-tert-butyl-phenyls）Phosphite ester, distearyl acidic group pentaerythritol diphosphites,
Phosphorous acid three（Single nonyl benzene and dinonyl benzene mixed ester）, three（Nonyl benzene）Phosphite ester, four [B-（3,5- di-t-butyl -4- hydroxyls
Base phenyl）Propanoic acid] pentaerythritol ester, B-（4- hydroxyl -3,5 di-tert-butyl-phenyls）Any one in the positive octadecanol ester of propanoic acid
Or it is several.
The thin-film solar cells preparation method of photocurable polyimide film of the present invention, comprises the steps：
（1）By polyimides；Nanometer aluminium powder；Light curing agent；Antioxidant；Hindered amine light stabilizer etc. with agitator-
Under 10 ~ 40 DEG C of temperature environments, blended under agitation is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control is squeezed at 220 ~ 290 DEG C
Go out thing Jing to filter, measure extrusion, curtain coating, cooling, drawing-off, traction, coiling process, obtain flexibility or thin-film solar cells are used up
Cure polyimide film.
Beneficial effects of the present invention：Nano metal aluminum particulate is easy to passivation, although can change shapes and sizes, after passivation
Nanoparticle attribute change very little.Nanoparticle has rough surface, and scattering light can more enter wide spectrum wavelength model
Enclose.This can bring bigger absorption, so as to improve the whole efficiency of battery.The scattering of metal aluminum nanoparticles increased light stop
Time in the film, the light of overall absorption is made to reach a kind of level, can match in excellence or beauty traditional solaode.Jing uses this
Thin film solar electricity of the thin-film solar cells ratio of Mingguang City's cure polyimide film process without this photocurable polyimide film
Pond performance improves 3-15%.Using this with after photocurable polyimide film, metal aluminum nanoparticles can draw thin-film solar cells
It is guide-lighting preferably to enter solaode, prevent light from escaping.Solve in traditional " thick film " solaode, nanoparticle does not have
What effect and all of light absorption must rely on the problem of thickness solution.
Specific embodiment
Embodiment 1
（1）By polyimides（Ningbo Jinshan Electronic Materials Co., Ltd）100 Kg；Nanometer aluminium powder 0.0001Kg；Crosslinking is solid
Agent（2,5- dimethyl -2,5 pairs（T-butyl peroxy）Hexane）0.8Kg；UV absorbers（- 4 methoxyl group hexichol first of 2- hydroxyls
Ketone）0.1 Kg；Antioxidant（Four [B-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] pentaerythritol ester）0.1 Kg；Amine light
Stabilizer（It is double（1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls）Last of the ten Heavenly stems diester）0.2 Kg, it is warm at -10-5 DEG C with agitator
Under degree environment, blended under agitation is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 250 DEG C, extrudate
180 mesh filters of Jing are filtered, metering extrusion（Dosing pump turnover pressure differential is 2MPa）, curtain coating film thickness 50UM, 10 DEG C of air it is cold
But, 4 times of degree of draft drawing-offs, release paper overlay films, the operation such as batch, obtain a kind of flexible or thin-film solar cells light-solidifying poly
Acid imide film.Jing improves 3.6% than untapped thin-film solar cells performance using the thin-film solar cells of this thin film.
Embodiment 2
（1）By polyimides（Ningbo Jinshan Electronic Materials Co., Ltd）100 Kg；0.1 Kg of nanometer aluminium powder；Crosslinking curing
Agent（2,5- dimethyl -2,5 pairs（T-butyl peroxy）Hexane）0.5 Kg；UV absorbers（- 4 methoxyl group hexichol first of 2- hydroxyls
Ketone）0.12 Kg；Antioxidant（Three（Nonyl benzene）Phosphite ester）0.2 Kg；Amine light stabilizer（It is double（1- octyloxy -2,2,6,6-
Tetramethyl -4- piperidyls）Last of the ten Heavenly stems diester）0.1 Kg, with agitator, under -10-40 DEG C of temperature environment, blended under agitation is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 230 DEG C, extrudate
180 mesh filters of Jing are filtered, metering extrusion（Dosing pump turnover pressure differential is 2MPa）, curtain coating film thickness 50UM, 10 DEG C of air it is cold
But, 4 times of degree of draft drawing-offs, release paper overlay films, the operation such as batch, obtain a kind of flexible or thin-film solar cells light-solidifying poly
Acid imide film.Jing improves 6.6% than untapped thin-film solar cells performance using the thin-film solar cells of this thin film.
Embodiment 3
（1）Polyimides（Ningbo Jinshan Electronic Materials Co., Ltd）100 Kg；Nanometer aluminium powder, 0.05Kg；Crosslinking curing
Agent（1,1-（Double tert-butyl peroxides）3,3,5- trimethyl-cyclohexanes）1.25Kg；UV absorbers（The just pungent oxygen of 2- hydroxyls -4
Base benzophenone）0.16 Kg；Antioxidant（Phosphorous acid three（Single nonyl benzene and dinonyl benzene）Mixed ester）0.15 Kg；Amine light is steady
Determine agent（（2,2,6,6- tetramethyl -4- piperidyls）Sebacate）0.15 Kg, is stirred under 0-10 DEG C of temperature environment with agitator
Blending is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 220 DEG C, extrudate
180 mesh filters of Jing are filtered, metering extrusion（Dosing pump turnover pressure differential is 2MPa）, curtain coating film thickness 50UM, 10 DEG C of air it is cold
But, 4 times of degree of draft drawing-offs, release paper overlay films, the operation such as batch, obtain a kind of flexible or thin-film solar cells light-solidifying poly
Acid imide film.
Jing improves 14.8% than untapped thin-film solar cells performance using the thin-film solar cells of this thin film.
Embodiment 4
（1）By polyimides（Changchun applied chemistry institute）100 Kg；0.008 Kg of nanometer aluminium powder；Crosslinking and curing agent（1,1-
（Double tert-butyl peroxides）3,3,5- trimethyl-cyclohexanes）1.0 Kg；UV absorbers（[4,5- is double for 2-（2,4- dimethyl benzenes
Base）- 1,3,5- triazine -2- bases] -5-（Octyloxy）Phenol）0.18 Kg；Antioxidant（Distearyl acidic group tetramethylolmethane diphosphorous acid
Ester）0.18Kg；Amine light stabilizer（Poly-succinic（- 1 piperidine ethanol of 4 hydroxyl -2,2,6,6- tetramethyls）Ester）0.12 Kg, uses
Agitator blended under agitation under 10-20 DEG C of temperature environment is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 260 DEG C, extrudate
180 mesh filters of Jing are filtered, metering extrusion（Dosing pump turnover pressure differential is 2MPa）, curtain coating film thickness 50UM, 10 DEG C of air it is cold
But, 4 times of degree of draft drawing-offs, release paper overlay films, the operation such as batch, obtain a kind of flexible or thin-film solar cells light-solidifying poly
Acid imide film.
Jing improves 8.2% than untapped thin-film solar cells performance using the thin-film solar cells of this thin film.
Embodiment 5
（1）By polyimides（Changchun applied chemistry institute）100 Kg；0.002 Kg of nanometer aluminium powder；Crosslinking and curing agent（Tertiary fourth
Base peroxide 2- ethylhexyl carbonates）1.2 Kg；UV absorbers（[4,5- is double for 2-（2,4- 3,5-dimethylphenyls）- 1,3,5- three
Piperazine -2- bases] -5-（Octyloxy）Phenol）0.2 Kg；Antioxidant（Three（2,4- di-tert-butyl-phenyls）Phosphite ester）0.12 Kg；Amine
Light stabilizer（Poly-succinic（- 1 piperidine ethanol of 4 hydroxyl -2,2,6,6- tetramethyls）Ester）0.18 Kg, with agitator at 30-40 DEG C
Under temperature environment, blended under agitation is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 290 DEG C, extrudate
180 mesh filters of Jing are filtered, metering extrusion（Dosing pump turnover pressure differential is 2MPa）, curtain coating film thickness 50UM, 10 DEG C of air it is cold
But, 4 times of degree of draft drawing-offs, release paper overlay films, the operation such as batch, obtain a kind of flexible or thin-film solar cells light-solidifying poly
Acid imide film, Jing improve 11.3% than untapped thin-film solar cells performance using the thin-film solar cells of this thin film.
Claims (6)
1. a kind of thin-film solar cells photocurable polyimide film, it is characterised in that including following weight parts such as the following group
Point：Polyimides 100；Nanometer aluminium powder 0.0001-0.1；Light curing agent 0.5 ~ 1.25；Antioxidant 0.1 ~ 0.2；Ultraviolet absorber
0.1~0.2；Amine light stabilizer 0.1 ~ 0.2；
Described polyimide resin is that Jing introduces fluorine-containing, silicon, the group of phosphorus or hydroxyl, or introduces lipid structure unit or employing
The monomer modified polyimide resin of backbone twist can be made.
2. thin-film solar cells according to claim 1 photocurable polyimide film, it is characterised in that：Described amine
Class light stabilizer is double（1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls）Last of the ten Heavenly stems diester or（2,2,6,6- tetramethyl -4- piperazines
Piperidinyl）Sebacate, poly-succinic（- 1 piperidinyl-acetate of 4- hydroxyl -2,2,6,6- tetramethyls）In one or more mixed
Close.
3. thin-film solar cells according to claim 1 photocurable polyimide film, it is characterised in that：Described light
Firming agent is aromatic carbonyl.
4. thin-film solar cells according to claim 1 photocurable polyimide film, it is characterised in that：Described light
Firming agent is phenyl ketone based compound.
5. thin-film solar cells according to claim 1 photocurable polyimide film, it is characterised in that：Described is anti-
Oxidant is three（2,4- di-tert-butyl-phenyls）Phosphite ester, distearyl acidic group pentaerythritol diphosphites, three（Nonyl benzene）
Phosphite ester, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] pentaerythritol ester, β-（4- hydroxyl -3,5 di-t-butyls
Phenyl）The positive octadecanol ester of propanoic acid or in any one or a few.
6. preparation method of the thin-film solar cells described in claim 1 with photocurable polyimide film, it is characterised in that：Bag
Include following steps：
（1）By polyimides, nanometer aluminium powder, light curing agent, antioxidant, ultraviolet absorber, amine light stabilizer agitator-
Under 10 ~ 40 DEG C of temperature environments, blended under agitation is uniform；
（2）Above blend importing screw mixes extruder is carried out into blending extrusion, temperature control at 220 ~ 290 DEG C, extrudate
Jing is filtered, is measured extrusion, curtain coating, cooling, drawing-off, coiling process, obtains flexibility or thin-film solar cells photocuring polyamides
Imines film.
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| WO2017014279A1 (en) * | 2015-07-22 | 2017-01-26 | 住友化学株式会社 | Resin film, layered body, optical member, display member, and front plate |
| JP2017119821A (en) | 2015-12-28 | 2017-07-06 | 宇部興産株式会社 | Polyimide material and method for producing the same |
| WO2018134976A1 (en) * | 2017-01-20 | 2018-07-26 | 住友化学株式会社 | Resin film, layered product, optical member, display member, and front panel |
| CN108455995A (en) * | 2018-02-09 | 2018-08-28 | 青海大学 | A kind of silicon carbide fibre enhancing aluminum phosphate ceramic matric composite and preparation method thereof |
| JP2019172894A (en) * | 2018-03-29 | 2019-10-10 | 信越化学工業株式会社 | Silicone-modified polyimide resin composition |
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| CN101201541A (en) * | 2006-10-24 | 2008-06-18 | 三星电子株式会社 | Method for forming organic layer pattern, organic layer pattern prepared by the same and organic memory devices comprising the pattern |
| CN102668108A (en) * | 2009-11-20 | 2012-09-12 | E.I.内穆尔杜邦公司 | Assemblies comprising a polyimide film and an electrode, and methods relating thereto |
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| CN101201541A (en) * | 2006-10-24 | 2008-06-18 | 三星电子株式会社 | Method for forming organic layer pattern, organic layer pattern prepared by the same and organic memory devices comprising the pattern |
| CN102668108A (en) * | 2009-11-20 | 2012-09-12 | E.I.内穆尔杜邦公司 | Assemblies comprising a polyimide film and an electrode, and methods relating thereto |
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