CN103897316B - Flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof - Google Patents

Flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof Download PDF

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Publication number
CN103897316B
CN103897316B CN201210587890.1A CN201210587890A CN103897316B CN 103897316 B CN103897316 B CN 103897316B CN 201210587890 A CN201210587890 A CN 201210587890A CN 103897316 B CN103897316 B CN 103897316B
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epoxy resin
thin
solar cells
fluorine richness
film solar
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CN103897316A (en
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张迎晨
吴红艳
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Zhongyuan University of Technology
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Zhongyuan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92609—Dimensions
    • B29C2948/92647—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92923—Calibration, after-treatment or cooling zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps

Abstract

A kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof, including the following component of following weight parts: fluorine richness epoxy resin 100；Nanometer aluminium powder 0.0001 0.1.Utilize that screw is blended, extrusion equipment is by fluorine richness epoxy resin；Nanometer aluminium powders etc. are blended, and extrude and import casting head through filtering, and cooled, drawing-off, the operation such as batch and obtain fluorine richness epoxy resin basement membrane used for solar batteries.Product out made by the present invention, invests thin-film solar cells light receiving surface or does the upper encapsulating film of solar cell, directly improves the flexible or generating efficiency of thin-film solar cells.

Description

Flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof
Technical field
The present invention relates to a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof, by using this film to be encapsulated in flexibility or the surface of thin-film solar cells incidence surface, directly improve the flexible or efficiency of thin-film solar cells.
Background technology
Special nature due to fluorine atom; fluoropolymer forms the F atom leptospira structure at periphery parcel C-C main chain, and C-F key is highly stable, and bond energy is 485 kJ/mol; fluorine atom is very tight in the arrangement of carbon skeleton outer layer, main chain and interior molecules can be formed shielding protection.Protection C-C main chain is not destroyed by severe environmental conditions, and keeps the stability of height.Containing the fluorine atom that sterically hindered less and electrophilic ability is stronger on organo-fluorine polymer material molecule side base or side chain so that it is surface free energy is the lowest, show the waterproof and oilproof of excellence, contaminated resistance.Therefore fluorocarbon coating has the special performance that some other coating hardly match, such as: fabulous weatherability, excellent chemical resistance, low abrasiveness, hydrophobicity, oil repellency, noninflammability etc., it is applied in many applications, is more and more paid close attention to by coating circle personage.
Epoxy resin has tack, heat endurance, chemical-resistant, insulating properties and the mechanical strength etc. of excellence, is widely used in the fields such as coating, adhesive and composite.Epoxy resin itself is insoluble in water, being not easy in water dispersion, aqueous epoxy emulsion to be prepared currently mainly has 3 kinds of methods: Mechanical Method, phase inversion (curing agent emulsion process) and chemic modified method. and wherein chemic modified method has plurality of advantages relative to first two method: need not additional emulsifying agent, water-fast solvent resistance height, emulsion particle diameter little (nanoscale), storage stability is good, state of cure is high, film dense uniform.In recent years, acrylic monomer is utilized to carry out graft modification epoxy resin, do not consume epoxy radicals and hydroxyl, the emulsion particle diameter obtained is little, emulsion intercalation method is good, both there are the high-modulus of epoxy resin, high intensity, chemicals-resistant and excellent anti-corrosive properties, there is again the features such as acrylic resin gloss, richness, good weatherability.Aqueous epoxy resins has the advantages such as excellent adhesive force, high-modulus, high intensity, chemical-resistant and anti-corrosive properties, utilize epoxy resin that fluorinated acrylate emulsion is carried out blending and modifying, water-fast, solvent resistant, adhesive force and the mechanical property of coating can be improved, under conditions of not affecting use requirement, coating cost is greatly lowered simultaneously.Wang Yifeng etc. are prepared for epoxy resin modification acrylate copolymer complex emulsions by physical blending process, fluorine-containing latex and epoxy emulsion are blended by the total root of Qin etc., when finding film forming, resin can be produced from layering, and the film so obtained has the surface property of excellence and good adhesion property.(1. Wang Yue is glad, Wang Jingke, Zhang Qian, Zhai He, Wang Fang, with the modification to epoxy coating of the epoxide group fluorinated copolymer, and " polymer material science and engineering " 2012 year 03 phase.2. Xu little dragon, Li Baosong, Wu Xuedong, Hexafluorobutyl mathacrylate grafted epoxy powdery paints studies, " coatings industry ", the 4th phase in 2010 56-59 page)
Effectively utilize in the middle of project at solar energy: solar photovoltaic utilization is the most with fastest developing speed, most active research field.The making of general solar cell is mainly based on semi-conducting material, utilizes photoelectric material that opto-electronic conversion reaction generating occurs after absorbing luminous energy.According to the difference of material therefor, solar cell can be divided into: 1, silicon solar cell；2, with multi-element compounds solar cells as material such as inorganic salts such as GaAs III-V compound, cadmium sulfide, CISs；3, the solar cell prepared with functional high molecule material；4, nano-crystalline solar battery etc..
What prior art operating efficiency was the highest is with Group III-V semiconductor inorganic material is raw-material product.Such as: the quantum well of GaAs/germanium single junction type falls into crystal structure, its photoelectric transformation efficiency up to > 18 %；And multiple junction quantum well falls into the solar cell of crystal structure, such as: InGaP/GaAs/germanium, its photoelectric transformation efficiency may be up to > 30 %.The most most widely used, based on silicon: to include non-crystalline silicon, photoelectric transformation efficiency about 9 %；Polysilicon, photoelectric transformation efficiency about 14 %；Monocrystalline silicon, photoelectric transformation efficiency about 17 %.Although in price, VI race elements Si is more cheap than Group III-V semiconductor GaAs, but its price manufactured, compared with macromolecule organic solar batteries, expensive many；And in application, the overall plasticization organic solar batteries of the anxiety of light weight crack-free again can realize via the processing of printing, in addition to price reduction, it is more suitable for the demand of portable electronic product, and all can normally use (this is that siliceous solar cell is beyond one's reach) at indoor or cloudy day so that its practicality and market application range more promote.
Solar cell is a key technology, can advance the production of energy more cleaned.But the Cost Problems of solar cell, reduces the economic competitiveness of heliotechnics.For overcoming this problem, thin-film solar cells is the technology being widely used at present, and can reduce the usage amount of expensive semi-conducting material in a large number, but the absorbing amount of thin-film solar cells is relatively low, and performance is less than traditional solar cell.
Thin-film solar module is made up of glass substrate, metal level, transparency conducting layer, electrical function box, glueing material, semiconductor layer etc..Organic-inorganic composite solar cell is solar cell based on organic conjugate polymer-inorganic nano-crystal composite system, because having high-molecular organic material good film-forming property simultaneously, level structure and band gap can easily be accommodated, low cost, large area, flexible solar battery device and inorganic nano-crystal material high stability can be prepared by wet method, high mobility, the advantages such as ordered nano-structure can be constructed, and become the study hotspot of area of solar cell in recent years.Metal nanoparticle can guide light preferably to enter solar cell, prevents light from escaping.In traditional " thick film " solar cell, nano particle does not has any effect, because all of light absorption is all by this film, this just relies on its thickness.But, for film, nano particle just can play great role.Their scattering adds light and stops the time in the film, makes the light of overall absorption reach a kind of level, and can match in excellence or beauty traditional solar cell.
Aluminium and Nano silver grain, in the frequency spectrum of visible part, can focus light into solar cell well.But optical resonance also results in nano particle absorbs light, and this means that the efficiency of solar cell can be relatively low.Nano grain of silver sub-resonance is just in solar cell key absorption spectrum part, so the absorption of light is appreciable.Aluminum nanoparticles resonates beyond solar cell key spectra part.Loss to energy is less, additionally, aluminum particulate is easy to passivation, although can change shapes and sizes, after passivation, nano particle attribute change is the least.Nano particle has rough surface, scattering light can enter wide spectrum wave-length coverage more.This can bring bigger absorption, thus improves the whole efficiency of battery.
Summary of the invention
It is an object of the invention to provide a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof, by using this film to be encapsulated in flexibility or the surface of thin-film solar cells incidence surface, directly improve the flexible or efficiency of thin-film solar cells.And have encapsulated flexibility or thin-film solar cells has self-cleaning effect.
For achieving the above object, the technical solution used in the present invention is as follows:
The flexibility of the present invention or thin-film solar cells fluorine richness epoxy resin film, including the following component of following weight parts: fluorine richness epoxy resin 100；Nanometer aluminium powder 0.0001-0.1.
Described fluorine richness epoxy resin refers to the mixing of one or more in the polyacrylic acid perfluoro alkyl ethyl with epoxide group, the polyacrylic acid perfluoro alkyl ethyl with epoxide group containing nano imvite, the Hexafluorobutyl mathacrylate epoxy resin containing nano-powder, bisphenol-A epoxy-Hexafluorobutyl mathacrylate resin, bisphenol-A epoxy-acrylic perfluoro alkyl ethyl resin.
The flexibility of the present invention or thin-film solar cells fluorine richness epoxy resin basement membrane, comprise the steps:
(1) by the fluorine richness asphalt mixtures modified by epoxy resin of formula ratio；Nanometer aluminium powder agitator blended under agitation under-10 ~ 40 DEG C of temperature environments is uniform；
(2) above blend is imported screw mixes extruder and carry out blending extrusion, temperature controls at 20-290 DEG C, extrudate through filtering, metering extrude, be cast, cool down, drawing-off, traction, coiling process, obtain flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.
The invention provides a kind of nanometer aluminium powder modification fluorine richness epoxy resin basement membrane, this film both can be used at the backlight of thin-film solar cells, can also be used in thin-film solar cells enters light film surface, the intermediate layer of thin-film solar cells can also be used in simultaneously, improve the efficiency of light absorption of solar cell.Improve the generating efficiency of solar cell.
Nano metal aluminum particulate is easy to passivation, although can change shapes and sizes, after passivation, nano particle attribute change is the least.Nano particle has rough surface, scattering light can enter wide spectrum wave-length coverage more.This can bring bigger absorption, thus improves the whole efficiency of battery.The scattering of metallic aluminium nano particle adds light and stops the time in the film, makes the light of overall absorption reach a kind of level, and can match in excellence or beauty traditional solar cell.Thin-film solar cells through using film of the present invention to process improves 3-15% than the thin-film solar cells performance processed without this film.After thin-film solar cells uses this film, metallic aluminium nano particle can guide light preferably to enter solar cell, prevents light from escaping.Solving in traditional " thick film " solar cell, nano particle does not has any effect and all of light absorption must rely on the problem that thickness solves.
Detailed description of the invention
Embodiment 1
By polyacrylic acid perfluoro alkyl ethyl 100 kg with epoxide group；Nanometer aluminium powder 0.02 kg agitator blended under agitation under 10 DEG C of temperature environments is uniform；Above blend is imported screw mixes extruder and carries out blending extrusion, temperature controls at 25 DEG C, extrudate filters through 100 mesh filters, pass in and out measuring pump pressure differential 1MPa metering extrusion, be cast out thick for 100UM casting films, 10 degree air coolings, 3 times of degree of draft drawing-offs, draw, the operation such as batch, and obtains a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.Through using the thin-film solar cells of this film to improve 15.2% than untapped thin-film solar cells performance.
Embodiment 2
By polyacrylic acid perfluoro alkyl ethyl 100 kg with epoxide group containing nano imvite；Nanometer aluminium powder 0.05 kg agitator blended under agitation under-10 DEG C of temperature environments is uniform；Above blend is imported screw mixes extruder and carries out blending extrusion, temperature controls at 290 DEG C, extrudate filters through 100 mesh filters, pass in and out measuring pump pressure differential 1MPa metering extrusion, be cast out thick for 100UM casting films, 10 degree air coolings, 3 times of degree of draft drawing-offs, draw, the operation such as batch, and obtains a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.Through using the thin-film solar cells of this film to improve 3.6% than untapped thin-film solar cells performance.
Embodiment 3
By Hexafluorobutyl mathacrylate epoxy resin 100 kg containing nano-powder；Nanometer aluminium powder 0.0001 kg agitator blended under agitation under 0 DEG C of temperature environment is uniform；Above blend is imported screw mixes extruder and carries out blending extrusion, temperature controls at 60 DEG C, extrudate filters through 100 mesh filters, pass in and out measuring pump pressure differential 1MPa metering extrusion, be cast out thick for 100UM casting films, 10 degree air coolings, 3 times of degree of draft drawing-offs, draw, the operation such as batch, and obtains a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.Through using the thin-film solar cells of this film to improve 8.8% than untapped thin-film solar cells performance.
Embodiment 4
By bisphenol-A epoxy-Hexafluorobutyl mathacrylate resin 100 kg；Nanometer aluminium powder 0.1 kg agitator blended under agitation under 40 DEG C of temperature environments is uniform；Above blend is imported screw mixes extruder and carries out blending extrusion, temperature controls at 20 DEG C, extrudate filters through 100 mesh filters, pass in and out measuring pump pressure differential 1MPa metering extrusion, be cast out thick for 100UM casting films, 10 degree air coolings, 3 times of degree of draft drawing-offs, draw, the operation such as batch, and obtains a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.Through using the thin-film solar cells of this film to improve 7.9% than untapped thin-film solar cells performance.
Embodiment 5
By bisphenol-A epoxy-acrylic perfluoro alkyl ethyl resin 100 kg；Nanometer aluminium powder 0.008 kg agitator blended under agitation under 10 DEG C of temperature environments is uniform；Above blend is imported screw mixes extruder and carries out blending extrusion, temperature controls at 25 DEG C, extrudate filters through 100 mesh filters, pass in and out measuring pump pressure differential 1MPa metering extrusion, be cast out thick for 100UM casting films, 10 degree air coolings, 3 times of degree of draft drawing-offs, draw, the operation such as batch, and obtains a kind of flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane.Through using the thin-film solar cells of this film to improve 9.2% than untapped thin-film solar cells performance.
Fluorine richness epoxy resin used in the embodiment of the present invention is all purchased from Yongzhou Li great resin raw material Co., Ltd.

Claims (2)

1. a flexibility or thin-film solar cells fluorine richness epoxy resin film, it is characterised in that: include the following component of following weight parts: fluorine richness epoxy resin 100；Nanometer aluminium powder 0.0001-0.1；
Described fluorine richness epoxy resin refers to the mixing of one or more in the polyacrylic acid perfluoro alkyl ethyl with epoxide group, the polyacrylic acid perfluoro alkyl ethyl with epoxide group containing nano imvite, the Hexafluorobutyl mathacrylate epoxy resin containing nano-powder, bisphenol-A epoxy-Hexafluorobutyl mathacrylate resin.
2. the flexibility described in claim 1 or the thin-film solar cells preparation method of fluorine richness epoxy resin film, it is characterised in that: comprise the steps:
(1) by the fluorine richness epoxy resin of formula ratio；Nanometer aluminium powder agitator blended under agitation under-10 ~ 40 DEG C of temperature environments is uniform；
(2) above blend is imported screw mixes extruder and carry out blending extrusion, temperature controls at 20-290 DEG C, extrudate through filtering, metering extrude, be cast, cool down, drawing-off, traction, coiling process, obtain flexibility or thin-film solar cells fluorine richness epoxy resin film.
CN201210587890.1A 2012-12-31 2012-12-31 Flexibility or thin-film solar cells fluorine richness epoxy resin basement membrane and preparation method thereof Expired - Fee Related CN103897316B (en)

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CN108565305A (en) * 2018-04-26 2018-09-21 徐州日托光伏科技有限公司 The manufacturing method of back contact solar cell

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CN102054878A (en) * 2009-10-27 2011-05-11 苏州中来太阳能材料技术有限公司 High barrier ultraviolet ray aging resistant solar cell back film and processing technique thereof
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