CN109121462A - Photovoltaic module backboard comprising thermoplastic vulcanizate composition - Google Patents

Abstract

It provided herein is comprising thermoplastic vulcanizates and/or the backboard made of thermoplastic vulcanizates, the PV module comprising such backboard based on TPV, and the method for forming the TPV backboard and PV module.Backboard based on TPV provides the particular advantage better than existing backboard, including increased flexibility, bigger electrical insulation capability and more it is desirable that barrier property.Some embodiments provide improved durability based on the backboard of TPV for PV module, especially even more so under the conditions of PV module is often configured at variation therein and frequent harsh environment.The backboard based on TPV of some embodiments can also effectively construct uncommon PV module geometry, such as non-planar (such as bending and/or hinged) geometry.

Description

Photovoltaic module backboard comprising thermoplastic vulcanizate composition

Inventor: Joseph G.Flendrig；Vincent A.Pirmez；With Ulf L.R.Nilsson

Related files statement

This application claims entitled " the Photovoltaic Module Back Sheets submitted on March 30th, 2016 The U.S. Provisional Application Serial No.62/ of Comprising Thermoplastic Vulcanizate Compositions " The priority for the European application No.16170981.1 that on May 24th, 315337 and 2016 submits.The application also in March, 2016 Entitled " the Thermoplastic Vulcanizate Compositions for Photovoltaic Cell submitted for 30th The U.S. Provisional Application Ser No.62/315329 of Applications " is related.

Invention field

This disclosure relates to photovoltaic devices, such as photovoltaic battery module.Specifically, this disclosure relates to thermoplastic vulcanizates group Close object, product and its manufacturing method, can be used for such photovoltaic devices, for example, as in photovoltaic battery module backboard and/ Or encapsulating material.

Background of invention

Photovoltaic (PV) module generally includes the PV battery for converting solar energy into electric energy.PV battery must be suited to for a long time Outdoor use；However, they can relatively easy wear and tear when for such outdoor use.Therefore, many common PV battery is located in glass and other encapsulating material protective layers.In general, transparent polymer material such as polyethylene vinyl acetate Ester (EVA) forms encapsulating material.However, being only inadequate in this way.Therefore, the plate that usually will be called " backboard " is administered to PV On rear side of battery (more specifically, being administered to the encapsulating material on rear side of PV battery), come help to protect the encapsulation PV battery (such as There is provided mechanical resistance, corrosion resistance, electrical insulating property, and to serve as the barrier etc. to various media (including water and other liquid) Other it is desirable that function).Such backboard is often laminated to the encapsulation of covering PV cell backside in battery manufacturing process On material (that is, with PV battery for side that trap the side of solar energy opposite).

Conventional backboard is usually formed by multilayer, and every layer for providing various forms of protections, (such as blocks moisture enters, machine Tool deformation, loss of charge etc.).Example includes three-layer structure, wherein polyethylene terephthalate (PET) layer by other two (each of which can independently be made of various other polymer compounds layer, such as Kynoar (PVDF) or other fluorine Polymer, ethylene vinyl acetate (EVA), polyethylene or a combination thereof) it surrounds.

Each of these Normal back plates construction is subject to various disadvantages.For example, multi-layer board is more complicated, and therefore usually It constructs more expensive.In addition, the risk being layered within the PV module life phase forms the increasing of the number of plies of backboard with being laminated together Add and increases.These backboards can also have higher than desired hardness, this makes them be easily broken and/or reduce PV module Flexibility.

(EPDM) rubber based on Ethylene-Propylene-Diene monomer has been proposed as selective rear side encapsulating material, Its defencive function that can also play backboard (such as not needing other back veneer material).See, for example, Kempe and Thapa, Low Cost, Single Layer Replacement for the Back-Sheet and Encapsulant Layers, Conf.Paper NREL/CP-520-42795 are held for August 10-14 days, SPIE PV Reliability in 2008 Symposium；United States Patent (USP) No.7902301；8183329.However, such backboard is not yet acceptable to the market, and they this There are adhesiveness and processing problems in external production PV module process.

Other interested bibliography include United States Patent (USP) No.2972600；3248179；3287440；4311628； 4387176；4540753；4543399；4588790；4594390；4613484；5001205；5028670；5100947； 5157081；5198401；5290866；5317036；5352749；5391629；5397832；5405922；5436304； 5453471；5462999；5616661；5627242；5656693；5665818；5668228；5677375；5693727； 5712352；5936028；5952425；6042260；6147160；6437030；6451915；6867260；6881800； 6992158；7232871；8895835 and 9006332；U.S. Patent Publication No.2002/0169240；2005/0107530； 2006/0269771；2007/0015877；2009/0247656；2010/0113694；2010/0298473；2010/ 0120953；2011/0041891；2012/0240981；2014/0076382；With 2014/0076395；EP patent disclosure No.2405489A1；EP0794200, EP0802202, EP0634421；Chinese patent discloses No.101469095A；Japan Patent Open No.H07-062168, H07-285143, H09-012799, H09-012800 and 2002-348430；And WIPO is disclosed No.WO96/08520；WO96/33227；WO97/22639；WO00/01745；WO00/01766；WO02/036651；WO03/ 046071；WO2004/074361；WO2004/009327；WO2005/092964；WO2008/076264；WO2008/124040； WO2009/032622；WO2009/153786；WO2011/046545；WO2012/030577.Other interested non-patent ginsengs Examining document includes: Ellul et al., " Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs ", Rubber Chemistry and Technology, volume 68,573-584 Page (1995)；And Rummens, " Long Term Accelerated Weathering Tests on ' Coupons ' to Develop New Classes of Backsheets ", Session 5CV.2.8, the 31st boundary European Photovoltaic Solar Energy Conference and Exhibition, the 2478-2481 pages (in September, 2015).

Summary of the invention

The inventors have discovered that certain thermoplastic vulcanizates (TPV) compositions and material can be used for forming photovoltaic electric Pond backboard.Therefore, in some respects, the present invention includes that the backboard based on TPV (that is, comprising one or more TPV, is made from it Those of or especially form substantially).Suitable TPV includes at least partly crosslinking being dispersed in continuous thermoplastic matrix Rubber phase (rubber grain of usually small crosslinking).In a particular embodiment, preferred rubber includes EPDM.This is continuous Thermoplastic matrix in some embodiments include thermoplastic polyolefin, such as polypropylene.Hardness is at least 55 shore A, excellent The TPV of choosing at least 70 shore A is particularly suitable to form the backboard of the various embodiments according to this paper.It is preferred that such TPV is in addition Ground in the modulus of 100% elongation (" M100 ") is instead 1-15MPa, more preferable 1-6MPa, in PV module Show desired flexibility.

It is preferably 0.1- in various embodiments according to the average thickness of the backboard based on TPV of some embodiments 2mm, such as 0.1-1.5mm or 0.20-0.40mm.Remaining size (highly with one of width or the two) of the plate can It is suitble to the needs of application with respective change, is, for example, 5cm-5m, 10m or even more big.

In another aspect, the present invention includes photovoltaic (PV) module, retouched it includes one or more PV batteries and according to aforementioned The one or more backboards stated.The PV battery of some embodiments is at least partially enclosed in one or more encapsulating materials. The PV module of some embodiments includes preceding encapsulating material layer and post package material layer, can be mutually the same or different.It should Preceding encapsulating material layer is at least partly transparent for incident electromagnetic radiation；The post package material layer can be it is transparent, but It is necessarily transparent.It is preferred that the backboard of some embodiments and post package material layer contacts.It is further preferred that these embodiments Certain backboards also at least partly adhere to post package material layer.Equally, various aspects additionally provide to form such PV The method of module, including the backboard based on TPV is adhered to PV battery and/or encapsulating material layer, as a part of this method, To form PV module.

Another further aspect includes having the PV module of non-planar and/or hinged geometry.For example, according to some embodiment party The hinged PV module of case includes single continuously based on the backboard of TPV, with the multiple of (and being attached thereto) disposed thereon PV modular assembly.Each PV modular assembly includes the PV battery being at least partially enclosed in encapsulating material, and preferably further Include foreboard and side frame.The foreboard and side frame can make PV modular assembly substantially rigid；Additionally or instead, it can choose The encapsulating material is substantially rigid to make PV modular assembly, it may not be necessary to foreboard and/or side frame.The PV modular assembly is to pass through position Hinged space at one or more articulated positions along backboard separates.The articulated position is preferably can be changed hinged Position, this enables the backboard to fold at each articulated position, for example, accordion fashion, this makes PV module foldable For transport purposes, or it is configured to non-planar geometry, needs one or more between preceding (such as face light) surface A angle.

Attached drawing briefly describes

Fig. 1 is the diagram according to the disconnection pattern of the PV module of some embodiments of the disclosure.

Fig. 2 a is the side view according to the non-planar PV module with concave curve of some embodiments.

Fig. 2 b is the side view according to the hinged PV module of some embodiments of the disclosure.

Fig. 2 c is showing the side view of the folded range of the hinged PV module according to some embodiments of the disclosure.

Fig. 2 d is the side view according to the hinged PV module of some embodiments of the disclosure.

Fig. 3 is showing after applying 0,1 and 4 minute sided corona treatment respectively to sample, for being laminated to encapsulating material On the backboard based on TPV various samples standardized peeling force figure.

Fig. 4 is showing the figure of the peeling force needed for different temperature condition zonal testing plates.

Fig. 5 is showing after test board is exposed to wet heat condition 1000h, in different temperature condition zonal testing plate institutes The figure of the peeling force needed.

Fig. 6 is showing after test board is exposed to wet heat condition 2000h, in different temperature condition zonal testing plate institutes The figure of the peeling force needed.

Fig. 7 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Fig. 8 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Fig. 9 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Figure 10 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Figure 11 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Figure 12 is showing the change of the electrical property of the test PV module of the function as the time for being exposed to wet heat condition Figure.

Figure 13 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent hair in the PV battery in PV module Light figure.

Figure 14 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent of the PV battery in PV module Figure.

Figure 15 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent of the PV battery in PV module Figure.

Figure 16 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent of the PV battery in PV module Figure.

Figure 17 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent of the PV battery in PV module Figure.

Figure 18 is showing in the different time for being exposed to wet heat condition, tests the electroluminescent of the PV battery in PV module Figure.

Exemplary implementation scheme is described in detail

Definition

It is described below and is suitable for the definition of the invention described at present, and is related to certain embodiments of the present invention Some performances measurement method.

" photovoltaic cell " or " PV battery " is the electronic device that electromagnetic radiation can be converted to electric energy.Common PV electricity Pond includes the light active material (one or more) for capableing of absorption of electromagnetic radiation, and can be used for electromagnetic radiation being converted to electric energy Charge transport materials (one or more) (it can be the material same or different with light active material).

" photovoltaic module " or " PV module " is any device comprising at least one PV battery.Common PV module includes Some form of shell and/or encapsulating material protect PV battery.

When it is related to PV module and/or PV battery come in use, " front " of battery or module indicate the module and/or Surface as battery, when the module and/or battery are used for its intended applications (such as convert incident electromagnetic radiation When at electric energy) it is at the most direct incidence of the electromagnetic radiation entered." back side " of PV module and/or PV battery should refer to relatively Surface.

As used herein, any electromagnetic radiation that PV battery can be converted to electric energy can be referred to as " light ".This use Do not mean that such radiation is necessarily limited to the visible spectrum of electromagnetic radiation.

As used herein, the percentage or weight percent and wppm of wt% expression weight indicate part/million Part, it is based on weight.Unless otherwise directed, otherwise percentage and ppm value are considered to be wt% and wppm.

Referenced herein polymer includes various monomeric units, such as the unit of ethylene derivative, ethylene unit, or Abbreviation ethylene.In the case where polymer is referred to as comprising " ethylene unit " or " ethylene ", it should be understood that it indicates the polymerization Object includes " unit of ethylene derivative ", that is, the ethylene (- CH of the polymerized form in it₂CH₂-).This is equally applicable to refer to structure At any other monomeric unit (such as unit of propylene or propylene derived) of polymer.

As used herein, term " elastomer " refers to the combination of any polymer or polymer, meets ASTM The definition of D1566: " material, can be from big recoverable force, and can or change to such state, at this State its essentially insoluble (but can be swollen) is in boiling solvent ".As used herein, term " elastomer " can be with art Language " rubber " is used interchangeably.

Term " thermoplastic vulcanizates " or " TPV " are any such material by broad definition comprising are dispersed in The rubber components at least partly vulcanized in continuous thermoplastic matrix.Suitable TPV material may further include other at Point, such as one or more oil and/or other additives.

Term " vulcanized rubber " indicates such composition comprising some vulcanized components (such as rubber).Art Language " vulcanization " is defined in this paper with its widest meaning, and is commonly referred to as the composition in all or part The state of the composition after the vulcanization of some degree or amount has been carried out in (such as cross-linking rubber).Therefore, the term Comprising partly both with complete cure, and the also any type of solidification (crosslinking) comprising can be used for dynamic vulcanization --- It is heat, chemical or otherwise.

Preferred vulcanization type is " dynamic vulcanization ".Term " dynamic vulcanization ", which indicates to be blended, the curable of thermoplastic resin Rubber is being enough to be plasticized the vulcanization or solidification of the temperature of the mixture in a shear condition.In preferred embodiments, the rubber Glue is crosslinked simultaneously and is dispersed in thermoplastic resin with micrometer-sized particles.Depending on curing degree, rubber and thermoplastic resin The ratio between, the compatibility of rubber and thermoplastic resin, kneader type and mixing intensity (shear rate), other forms are for example being moulded Co-continuous rubber phase is possible in property matrix.

As used herein, " partial vulcanization " rubber is such rubber, wherein vulcanization (preferably dynamic vulcanization) it Afterwards, such as after the crosslinking of the rubber phase of TPV, the cross-linking rubber greater than 5 weight % (wt%) is can be in boiling xylene It extracts.For example, in the TPV of the rubber comprising partial vulcanization, at least 5wt% and less than 10,20,30 or 50wt% ( In various embodiments) cross-linking rubber be that extractible from TPV sample in boiling xylene (wt% is based on The total weight of rubber present in the TPV sample).Can percentage of the sol rubber in cured composition be by boiling two Sample described in reflux in toluene, the residue for weighing dry and based on the understanding to the composition come to the progress of solvable and indissolvable component It is suitable to correct to measure.Therefore, the initial and final weight of correction is removed by subtracting from the initial weight of soluble constituent Except the rubber to be vulcanized component (such as extending oil, the component for dissolving in organic solvent of plasticizer and the composition, with And it is not intended to cured thermoplastic component) come what is obtained.Any insoluble pigment is subtracted from initial and final weight the two, is filled out Material etc..When calculating the percentage of soluble rubber in solidification composition filling, dissolved in from being subtracted in rubber in uncured rubber Any material in reflux dimethylbenzene.The further description of technology about the percentage for measuring extractable rubber is special in the U.S. Sharp the 4th column 19-50 row of No.4311628 illustrates, from there through being incorporated by.

As used herein, it is such rubber that rubber, which (is either fully cured or fully crosslinked), in " complete cure " Glue, wherein after vulcanization (preferably dynamic vulcanization), such as after the rubber phase crosslinking of TPV, the cross-linking rubber less than 5wt% It can be extracted in boiling xylene.For example, in the TPV of the rubber comprising complete cure, less than 4,3,2 or even The cross-linking rubber of 1wt% is extractible from TPV sample in boiling xylene.In some embodiments, comprising In the TPV of the rubber of complete cure, 0.5-2.0wt%, such as the cross-linking rubber of 0.1-2.0wt% is in boiling xylene It is extractible from TPV sample.

Therefore, it can have less than 20,15,10,5,4,3,2 according to the TPV of various embodiments or even 1wt% The cross-linking rubber that can be extracted from TPV sample in boiling xylene, and at least 0.0,0.1 or 0.5wt%'s can be The rubber that boiling xylene extracts.

As used herein, " extending oil " can have similar composition with " processing oil ", or selected from same or similar Compound.The term is used to distinguish the opportunity of the introducing of oil described in elastic composition (including the TPV) manufacturing cycle." increment Oil as oil " is added elastomer after elastomer polymerization or is concomitantly introduced into elastomer, such as elastomer grain A part (together with any other desired additive) of material, construction materials contract etc. introduces, the transport such as the elastomeric pellets, construction materials contract or It provides to downstream manufacturer, which transfers for the elastomer to be processed into intermediate products (including TPV) and/or final goods. " processing oil " or " technical oil " be in such downstream manufacturing process (such as the extrusion in elastomer, mixing or other add During work, including forming TPV) prepared with elastomer.In the case where the oil content for describing TPV formulation herein, It is intended to the amount for being merely representative of the processing oil being added in the TPV formulation, as by one or more elastomers and one kind Or a variety of thermoplastic resins form a part of the method for TPV；Be likely to be present in be used to form TPV elastomer it is (a kind of or more Kind) in any extending oil be not included in such record.

As used herein, " Group I oil ", " Group II oil ", " Group III oil ", " Group IV oil " (also referred to as poly- α alkene Hydrocarbon or " PAO ") and " Group V oil " refer respectively to the base stock oil classification according to American Petroleum Institute (API) (in API 1509 attachment E, are illustrated in annex 1 (in March, 2015), are incorporated herein by reference by the 17th edition) the base stock oil that is understood Group.For example, Group I oil is the base oil or base stock oil of petroleum resources, has and be less than 90wt% saturate (according to ASTM D2007 measurement), sulphur greater than 300wppm (according to ASTM D1552, ASTM D2622, ASTM D3120, ASTM D4294 or Person ASTM D4297 measurement, and it is subject to ASTM D4294 in the case where the result of those methods contradicts), and have The viscosity index (VI) (being measured by ASTM D2270) of 80-120.Equally, Group II oil is the base oil or substantially former of petroleum resources Material oil, has and is greater than or equal to 90wt% saturate, the viscosity of sulfur content and 80-120 less than or equal to 300wppm Index (every kind of performance is by measuring with identical method specified by Group I oil).Section III, as IV and V group oils with Their descriptions in the attachment E of API 1509 are consistent.

Photovoltaic module

The disclosure includes photovoltaic (PV) module, sometimes referred to as solar panel in various embodiments, is had Backboard comprising thermoplastic vulcanizates (TPV).Backboard and be suitable as backboard TPV further details (including ingredient And formed) be discussed more fully below.

Disconnection such as Fig. 1 is diagrammatically shown, and the PV module according to some embodiments may include cladding plate or foreboard 101, It is at least partly transparent for incidence electromagnetic radiation (such as light).The transparency of foreboard is the bigger the better.Such as Fig. 1 institute Show, foreboard 101 is glass, although other materials (such as transparent polymer material such as polyethylene) can replace to form this Foreboard.In addition, may include protective coating etc. according to the foreboard of some embodiments, such as to provide scratch-resistant or fouling Property (Fig. 1 is not shown).Foreboard can be optionally omitted according to the PV module of still other embodiments (such as to beg in further detail below The case where preceding encapsulating material layer 105 of opinion provides the protection for the element that enough anti-PV modules will be used in environment therein In).

If it does, being the battle array for the PV battery 110 being at least partially enclosed in encapsulating material below the foreboard 101 Column, as shown in Figure 1, the encapsulating material includes preceding encapsulating material layer 105 and post package material layer 115.Preceding encapsulating material layer 105 wraps Containing preceding encapsulating material, and it is preferably similar to foreboard 101, is at least partly transparent for electromagnetic radiation.Post package material layer 115 include post package material.Different from preceding encapsulating material layer 105, post package material layer 115 can with but be necessarily transparent. Therefore, which can have same or different composition and some embodiment party in some embodiments The encapsulating material of case can be commonly described as including at least partly transparent preceding envelope for coating one or more PV battery front surface Package material, and the post package material of coating one or more PV battery rear surface.One or both of the front and rear encapsulating material can At least partly to cover the side of PV battery.Suitable encapsulating material (one or both of front and rear encapsulating material) is below more It describes in detail.

Finally, substrate or backboard 120 are contacted at least part of post package material layer 115, and preferably it is else adhered to Thereon.Foreboard 101 and backboard 120 sandwich the PV battery (one or more) of encapsulation in module 100.According to disclosed herein The backboard of embodiment includes TPV, is made from it or is consisting essentially of.Suitable TPV and the method that they form backboard It is more fully described after being further discussed encapsulating material below.When being used for context, when the backboard includes Non- TPV less than 5wt% material (for example including for the TPV post-processing (including the TPV formed backboard) processing oil, And including impurity or other materials, so that with only including TPV, and other identical performances of identical backboard of aspect Compare, with it is such oil, impurity and/or material the measurable performance change of backboard no more than it is +/- 5%) when, the backboard " being made of substantially TPV ".

According to the PV module of some embodiments can also include side frame 130, can by any suitable material (such as Aluminium, other metals, thermoplastic material etc.) it is made.Side frame can protect the inside modules (such as the He of encapsulating material 105 and 115 PV battery 110).The module can also include sealant systems 131 between frame and the layer of module, come help prevent pollutant into Enter and/or adheres to side frame on one or more layers of module.Any of suitable sealant systems can be used, wrap Include compound for example based on butyl.

The PV battery 110 of Fig. 1 is directly or indirectly to be electrically connected in terminal box 111.Other embodiments may include one PV battery (one or more) 110 is connected to external circuit (necessarily including terminal box 111) by a or multiple electric leads.It is general Lead to the skilled person will understand that by using any suitable live wire or other devices, by PV battery (one or more) 110 are electrically connected to many devices of external circuit, storage device (such as capacitor) etc., are completely in PV provided by the invention In the range of module.In addition, according to the PV battery of various embodiments may include coating (such as aluminium paste or art technology Other coatings known to personnel).It include both coating and uncoated battery (such as its at least portion when " PV battery " is mentioned above The description for the PV battery being encapsulated in encapsulating material with dividing may include the uncoated battery encapsulated in this way and encapsulate in this way Both batteries of coating).

The encapsulating material and backboard of the PV module according to various embodiments will be discussed in more detail now.

Encapsulating material

As shown, preceding encapsulating material should be at least partly transparent.Encapsulating material includes transparent gathers before suitable Close object material, provide the electrical isolation of at least some degree for the PV battery and be protected from environmental contaminants (such as moisture, Other liquid and/or gas and particulate pollutant).It is preferred that the encapsulating material adheres to foreboard when being present in PV module On (such as glass).In general, it is known in the art or be later discovered that be suitable encapsulating material for PV battery any PV Battery packaging material should be the suitable preceding encapsulating material for the PV module of various embodiments herein.Known package material The example of material includes basis in United States Patent (USP) No.6093757, or described in the open source literature for being related to PV battery packaging material Those of.See, for example, Kempe et al., " Types of Encapsulant Materials and Physical Differences Between Them ", Nat ' l Renewable Energy Laboratory 2010, Ke Yi (recent visit 2016 is obtained on http://www1.eere.energy.gov/solar/pdfs/pvrw 2010_kempe.pdf On March 10, in).For example, the preceding encapsulating material may include polymer material, it includes one of following or a variety of: from poly- Object, thermoplastic polyurethane (TPU), polyvinyl butyral (PVB), dimethyl silicone polymer or poly- (dimethyl siloxane) (PDMS), ethylene vinyl acetate (EVA) and having and provides for PV battery for moisture and its good optical transmittance Any other polymer material of at least part of barrier of his gas, liquid and solid pollutant.In some specific embodiment parties In case, which be at least partly crosslinked in the PV module of assembling.Therefore, such embodiment is prepared Encapsulating material, (be discussed more fully below) before heating or other activation, including can hand over during PV module assembled The polymer material of connection.

Encapsulating material can be prepared with one or more encapsulating material additives, such as curing agent (such as peroxide phenol Resinoid etc.), UV light stabilizing agent (such as hindered amine), UV absorbers (such as benzotriazole), adhesion promoter (such as Trialkoxy silane) and/or free radical scavenger (such as phenol phosphonate ester, wherein there is peroxide firming agent or its What his free radical formed curing agent is especially useful).Some (such as curing agent) of these additives can be in PV module It is at least partly consumed in forming process.For example, when the encapsulating material formulation heats in PV module process, it is as follows Face is discussed in detail, and at least some curing agent can be in any crosslinkable polymer material present in encapsulating material formulation Crosslinking in be consumed.

Suitable post package material includes any material of encapsulating material before being suitable for.However, post package material can be with It additionally or instead include with polymerization seldom or without optical transmittance (that is, with seldom or without transparency) Object material, such as one of following or a variety of: EPDM, polyethylene terephthalate (PET), polyamide, polyvinyl fluoride, Polyvinylidene fluoride, Ethylene-Propylene-Diene (EPDM) rubber etc..

Preferred encapsulating material (front and rear) not only helps that PV battery (one or more) is protected to prevent the PV module life phase Between mechanical damage；They, which may also help in, protects the battery (one or more) to prevent from the PV battery for therein Harmful liquid, gas and solid in environment enter.Encapsulating material also provides temperature and electrical isolation, to help (one, PV battery Or multiple) it is in desired temperature range in operation, and furthermore help so that along from (one or more, PV battery It is a) desired conducting wire charge transmit maximize.

It is preferred that the encapsulating material (including front and rear encapsulating material layer) at least partly adhere to foreboard (if there is Words), on PV battery (one or more) and backboard whole three, by PV battery (one or more) during PV module life Fixed to substantially suitable place.Specifically, before which at least partly adheres to foreboard and each PV battery Surface, then encapsulating material at least partly adheres to the rear surface of backboard and each PV battery.In forming PV module process, One or both of the front and rear encapsulating material in some embodiments can be along PV battery (one or more) or PV electricity The side flow of pond matrix, by the PV battery (one or more) or PV cell substrate is encapsulated on side and front and rear On surface, to provide other stability for the battery.Advantageously, in certain embodiments, not needing binder will seal Package material (such as post package material, in the wherein rear embodiment different with preceding encapsulating material) is directly adhered on backboard. It is the feelings using the manufacture of laminated and heating means in wherein PV module according to the method for some formation PV modules in greater detail below It is especially true in condition.The adhesive layer that such direct adherency avoids difference (is frequently necessary to it to adhere to encapsulating material often Advise backboard on) extra cost and complexity.

Backboard based on TPV

As shown, the backboard of various embodiments includes TPV, is made from it or is consisting essentially of.

Preferred back plate thickness is about 0.10mm-15.00mm, most preferably 0.20-1.5mm, such as 0.25-0.40mm, Or 0.25-0.35mm, wherein it is also contemplated that biggish maximum endpoint taken office from any just described minimum endpoint Range (such as 0.20-0.35mm etc.).Thickness can pass through any well known standard (such as ISO 23529, ISO 3302-1 Deng) measure, but in the case where the thickness measurements variation obtained by different methods is greater than 0.01mm, it should with root According to ISO 23529:2010, subject to the thickness of Section of 7.1 (for measuring the method for being less than the size of 30mm) measurement, condition is it In the thickness that measures by this method change from a position to another location greater than 0.01mm along plate surface, thickness should Take the average thickness (arithmetic average) along the measured value at 5 different locations of back plate surface.In addition, there is one in the plate Or in the case where multiple articulated positions (being explained in detail below), average thickness should be in the point for not being located at one of articulated position of the backboard Place's measurement.

The other sizes (such as length, width) of suitable backboard can be widely varied.For example, in various embodiments In, any one can be short to 5cm and grow to 5m length and width, or even longer.It is preferred that length and/or width are 20cm- 5m, such as 30cm-2m or 30cm-1.6m.Suitable backboard size can be square (such as 1m x 1m), rectangle (example Such as 1m x 1.6m), round (having the diameter according to above-mentioned length and/or width) or any other shape (have basis The maximum length and/or width along such shape of foregoing description).

Backboard those of (that is, comprising one or more TPV, be made from it or be consisting essentially of) based on TPV mentions The apparent benefit compared with Normal back plate material is supplied.There are various function for PV module according to the backboard of some embodiments Can, including electrical isolation and mechanical protection (such as prevent impact, puncture, clast entrance).Backboard can also advantageously act as barrier Object comes resistant to liquids and/or gas pollutant.Although in some cases, it is believed that obstructing such pollutant completely can be expectation , but can be more preferably the backboard ensure all undesirable materials (its be in module production process or it Normal use process in generated in encapsulating material) can be escaped from PV module.For example, in the encapsulating material formulation packet In the case where including crosslinkable polymer material (and more specifically, further including one or more curing agent), such material can It can be at least partly crosslinked during PV module making.In addition, some uncrosslinked polymer and solid after PV module making Agent is retained in encapsulating material to some extent, can be further crosslinked when the module is configured to working site. For example, heat, moisture and/or the radiation that cross-linking encapsulating material is exposed to it are bigger, which may more occur. These cross-linking reactions can produce by-product, can negatively affect the operation of the PV battery of encapsulation --- and it especially ought be in this way By-product it is even more so when being swept along in encapsulating material by PV battery.For example, the cross-linking reaction based on peroxide is considered The by-product that can corrode the metal side frame of some PV modules is produced, so that PV inside modules part is exposed to environmental contaminants. It is desirable, therefore, to which the backboard allows such by-product to migrate out the module.However, simultaneously, the backboard is preferably anti- Only undesirable pollutant (such as moisture) enters PV module from the environment that the module is placed in one, or alternatively, Even if the backboard allows such pollutant to enter PV module, which is also easy they module is discharged.For example, some In embodiment, the backboard based on TPV can permit a degree of moisture raised temperature (such as especially in PV module When high temperature exposure in operating process) enter, once but furthermore temperature is cooling, then moisture is discharged.Therefore, backboard can be advantageous Ground shows selective barrier property, rather than serving as complete barrier and/or backboard can advantageously allow for pollutant at certain It is migrated out (such as water or vapor are escaped in raised temperature) in a little conditioning process from PV battery, rather than other are (to prevent Undesirable entrance).

Show it is such it is desirable that the backboard of barrier property can advantageously extend the useful life of PV module.For To solve in all possible pollutants and backboard complexity involved in various desired barrier properties of competitiveness most Smallization, damp and hot (D-H) test can assist in whether backboard provides an advantage in that.Damp and hot test, such as following implementation It is described in detail in example part, including sample P V module is exposed to harsh environment condition and monitors the various performance (examples of the module Such as maximum admissible voltage, exported in the modular power of maximum power point, block coupled in series resistance and module short circuit electric current) or Backboard (such as adhesion strength with encapsulating material), which carrys out evaluation module, will continue acceptably to carry out solar energy to electrical conversion Time.The D-H test of this paper is carried out according to the agreement of damp and hot test is used for described in IEC 61215, in addition to having In the case where instruction, used be not the so-called 1000h exposure in IEC 61215 time (such as 2000h or even 3000h)。

Therefore, the base according to various embodiments is shown by the damp and hot test of success described in the following examples In the advantageous barrier property of the backboard of TPV, and further it is summarised in the PV mould below according to some embodiments of the invention In the discussion of the advantageous performance of block.

As another example, Normal back plate is greater than according to the flexibility of the backboard based on TPV of some embodiments, such as The backboard TPV of backboard (and/or formed) by this based on TPV 100% elongation modulus (" M100 ") come what is indicated. This high flexible (low stiffness) means (such as to return when PV module is expanded or shunk due to the result of module temperature difference Because replacing in round the clock with the four seasons), power needed for expanding or shrinking the plate will be power that is low, and therefore will not be increased by excessive Onto the total stress acted in the module.Compared with conventional PV module, this reduced expansion/convergent force can improve basis The service life of the PV module of various embodiments.It is used to form the preferred TPV of the backboard based on TPV according to some embodiments M100 value be related to being used to form based on the description of the suitable TPV of the backboard of TPV below and discuss in more detail.

Another advantage provided by the flexibility of the backboard based on TPV be for it is hinged or have non-planar geometric form A possibility that other PV modules of shape.As used herein, when any side on the cross section of PV module show it is non-planar When profile, which has " non-planar geometry ".For example, the PV module according to some embodiments can be made to have There are convex surface or concave curvature (front surface perhaps face optical surface) relative to module or some other molded non-planars, example Tathagata cooperates various desired configuration geometries.For example, Fig. 2 a shows the PV module 290 with concave geometry.This The module of sample can be by flexible and/or forming component (such as flexible or forming foreboard 291 and the flexible back based on TPV The PV battery 293 being encapsulated in encapsulating material 292 is clipped in wherein by plate 295) it generates.According to the various embodiments of this paper Therefore backboard based on TPV obtains many possibilities for flexible PV module design.In addition, according to still other embodiments PV module can be or including hinged PV module.According to the example of the hinged PV module of some such embodiments Display in figure 2b, wherein one continuously the backboard 200 based on TPV (have articulated position 205) be connected to two rigidity On PV modular assembly 210 and 220, each (difference) includes the first He layered on the first and second encapsulating materials 213 and 223 Second foreboard 211 and 221, first and second groups of PV batteries 215 and 225 of each encapsulation.Each PV modular assembly can be further Including side frame, the side of PV modular assembly has been framed (Fig. 2 b is not shown).In still other embodiments there may be along The backboard based on TPV is greater than an articulated position, this allows the backboard based on TPV being connected to three or more phases To on the PV modular assembly of rigidity.Additionally, it should be appreciated that the articulated position 205 of these various embodiments is (in such as Fig. 2 b and other It is shown) it does not need to fix (such as with angle shown in Fig. 2 b) with special angle；The backboard 200 based on TPV can be easily deformed (such as fold relative to such as construction shown in Fig. 2 b or non-collapsible) increases or decreases the angle of articulated position 200, or Person is even laid flat it, and either even the first and second PV components are folded each other together (such as storing or transporting It is defeated).

Therefore, as shown in Figure 2 d, some embodiments further provide PV module (such as PV module 240 of Fig. 2 d), It has the single continuously backboard 251 based on TPV and multiple PV modular assemblies 260 placed on it.Each component 260 can be with According to foregoing is directed to the first and second components of example 210 and 220 described in Fig. 2 b.Component 260 is arranged along backboard 251, It is preferably disposed on the same side of backboard 251, there is hinged space (such as space 271,272,273) between each, each hinge Space is connect corresponding to the articulated position (such as being 251,252,253 respectively) along the backboard.When as shown in Figure 2 d, hinged space (such as space 271) in this way close to articulated position (such as position 251) when hinged space " correspond to " articulated position, That is, the mode allows articulated position to come between on front side of two PV modular assemblies that (i) is limited on hinged space either side Angle, and/or (ii) are changeably folded along the articulated position, to be limited to two PV modular assemblies on hinged space either side The angle that can be changed between front side.The example of such angle is shown between each PV modular assembly 260 of Fig. 2 d；In addition, It is each hinged to limit that folding is shown by mobile arrow (showing that module 240 is the accordion fashion folded) in figure 2d The angle that can be changed at position 251,252 and 253.Alternatively, such articulated position enables module to extend and be laid flat (example Such as by along each articulated position axis fold, it is contrary with shown in Fig. 2 c).

Therefore, in short, each articulated position can changeably fold to limit the front surface of two adjacent PV modules components Between angle, the angle is about 0 ° -360 °, as shown in Fig. 2 c by a dotted line, which show backboard 200 along Articulated position 205 is unfolded, so that PV modular assembly 220 is kept fixed, while PV modular assembly 210 is along the dotted line institute of Fig. 2 c Show that path is unfolded.As used herein above and below angle such as herein by articulated position restriction, 0 ° of angle construction is to pass through arrangement The first and second PV modular assemblies 210 and 220 in Fig. 2 c are shown (that is, 0 ° of angle is defined as such construction, wherein PV module is folded around given articulated position itself, so that the front surface of the two PV modular assembly adjacent with articulated position It is facing with each other).Therefore, 180 ° of angle constructions are defined as flat arrangement of the PV module around given articulated position, so that the PV The modular assembly front surface both adjacent with articulated position faces same direction；Such cloth is defined with 360 ° of angle constructions It sets, the two of them PV modular assembly front surface adjacent with given articulated position faces opposite direction each other.The definition of these angles It is to be marked along folded/expanded circular path shown in Fig. 2 c.The backboard based on TPV advantageouslys allow for such variable Geometry, the backboard that also serves as (that is, the function of can still act as conventional PV module backplane simultaneously).

Furthermore, it is possible to which forming the single of some such embodiments is continuously advantageously had based on the backboard of TPV Along the variable thickness of the plate length.For example, other calendering or other compactings can be used for so that should the backboard based on TPV In articulated position, (such as articulated position 251,252 shown in Fig. 2 d and 253) thinner holds that the folding on such position more Easily, while the backboard being allowed to be connected to relative rigidity bigger at the position of PV modular assembly.In certain such embodiments In, continuously the average thickness of each articulated position of the backboard based on TPV can be the non-hinge of the continuously backboard based on TPV Connect the 90% or smaller of the average thickness of position, preferably 80% or smaller, or even 75% or smaller.

As described in detail below, another advantage of TPV material is in this way, that is, with include some of crosslinkable polymer material Backboard layer material (such as EVA) is compared, and is chemically stable, as long as they are crosslinked.Such conventional material have compared with Short storage life (such as in facility of PV module makers), this be attributed to due to being exposed to heat, moisture etc. at any time and A possibility that some crosslinkings occurred.By with longer storage life, various embodiments based on the backboard of TPV for Facilitate to reduce carrying cost for manufacturer and generates lower scrap rate.

Backboard based on TPV additionally provides the chance with the integration of PV module part.For example, part (connector, structure, His material) it may be molded directly on the backboard.The part that these are integrated is easy maintenance by the thermoplastic properties of the TPV And/or replacement.

Advantageously, according to the backboard of some embodiments include only a single layer, it includes the TPV (or substantially by It forms or is made from it).This is apparent simplification compared with some Normal back plates, and the Normal back plate constructs multiple layers (such as two or more of aramid layers, pet layer, PVF layers, PVDF layers, PE layers and EVA layer).

However, still another embodiment can instead include multilayer backboard, wherein at least one layer includes TPV (such as base It is multilayer materials in the backboard of TPV).The backboard based on TPV of such embodiment can be multi-layer composite materials Material, can advantageously replace the encapsulating material and backboard of conventional PV module.Therefore, the PV module of such embodiment includes The one or more PV batteries being at least partly encapsulated in multilayer materials.The multilayer materials include that (it is wrapped first layer Containing the TPV) and the second layer (it includes any materials for being suitable for post package material (as previously described)).By by the package material The function (and material) of material and backboard combines by this method, by allowing directly to encapsulate PV battery with backboard, without inserting respectively Enter encapsulating material layer, which still provides some simplification relative to conventional PV module, especially in PV mould Simplification in block manufacturing method.In addition, same supplier will provide the multilayer materials, this eliminates PV modular manufacture Quotient coordinates the needs of size and other consistency problems between the backboard and encapsulating material layer supplier of difference.

Similarly, in still another embodiment, backboard of the multilayer based on TPV may include one or more different from aforementioned The layer of the material of encapsulating material, on multiple-plate TPV layers of front side or rear side.For example, other polymers layer, packet It may include in such multilayer materials containing material such as thermoplastic material (such as polyethylene or polypropylene layer) On TPV layers of any or two sides.What such polymeric layer can provide target resists one or more expected environmental pollutions The protection of object such as moisture etc..

Therefore, include one or more other protective layers according to the PV module of some embodiments, be based on positioned at this The front side of the backboard of TPV and rear side it is any or both on, and/or the backboard based on TPV can be multilayer materials.

It is used to form the suitable TPV of the backboard based on TPV

The thermoplastic vulcanizates (TPV) for suitably forming the backboard of various embodiments includes to be dispersed in continuous thermoplasticity The rubber components at least partly vulcanized in matrix, the matrix include thermoplastic component.In some embodiments, the rubber group Point preferably complete cure or be fully cured.In addition, the rubber components are preferably in thermoplastic matrix with fine dispersion And fully dispersed particle form exist.

Such TPV is formed by dynamic vulcanization TPV formulation.The TPV formulation includes (i) rubber components, (ii) thermoplastic component, (iii) vulcanizing agent or curing agent；(iv) processing oil；(v) optional one or more additives (including such as curing accelerator, metal oxide, acid scavenger, fire retardant, filler, stabilizer etc.).The TPV therefore can be for Selection be characterized as be the dynamic vulcanization of the TPV formulation product.

By the formation for describing the TPV and its it is formed by performance first, suitable rubber components are then described in more detail, heat Plastic component, vulcanizing agent, processing oil and additive.

As understood by those skilled in the art, dynamic vulcanization includes method, and thus experience is mixed with thermoplastic resin Rubber is cured.The rubber is crosslinked or vulcanizes under high shear conditions in the temperature for being higher than thermoplastic resin fusing point.Make It is this method as a result, the thermoplastic resin becomes the continuous phase of mixture and the rubber becomes to be dispersed in the continuous thermoplastic Discontinuous phase in property phase.Therefore, in some embodiments, the mixture (such as the TPV formulation) is in dynamic vulcanization mistake It experienced phase reversal in journey, wherein the blend (it initially includes the rubber of large volume fraction) is converted to such blending Object, wherein Plastic phase is continuous phase, and rubber is crosslinked simultaneously and is dispersed in thermoplastic matrix as fine grained.

In general, the dynamic vulcanization of the TPV formulation occurs in the reactor.In addition, being not whole groups of the TPV formulation Divide and needs to be introduced into reactor simultaneously.

For example, progress of such as being got off according to the dynamic vulcanization of some embodiments: rubber components and thermoplastic component are mixed Form blend, can be referred to as solids blend (although not the whole components needs of the blend necessarily be in it is solid State).Optional solid additive (such as curing accelerator, filler, zinc oxide and various solids such as pigment and antioxidant) It can be added in the solids blend.The blend continuously mixes molten to be formed in the temperature for being higher than thermoplastic resin melting temperature Melt blend.Vulcanizing agent (such as curing agent), may be at solid or liquid form, introduce the melt blended material to be formed Vulcanizable blend.Continuous heating and mixing are to realize dynamic vulcanization.

Processing oil can introduce in any stage of the method or in multiple stages.For example, oil can be with curing agent Solids blend is added together, melt blended material is either added after dynamic vulcanization --- or in the aforementioned point of this method Any two or more additions.

After dynamic vulcanization, mixing can continue, and other additive or ingredient can introduce melting production In object, the thermoplastic vulcanizates of melting can be referred to as.For example, after cure additive such as acid is removed after dynamic vulcanization Agent can be added in melt substance.The product may then pass through extruder die head extrusion, or otherwise make, and most It cools down afterwards for handling and/or being further processed.For example, the thermoplastic vulcanizate composition of melting can be cooled down and/or be coagulated Gu and subsequent be granulated stores and/or is transported for future.Practice of the invention is not necessarily limited to before forming back veneer material, heat The mode that plasticity vulcanized rubber composition is then solidified or made.

Dynamic vulcanization method as described herein can be in continuous mixing reactor (it may also be referred to as continuous mixing device) It carries out.Continuous mixing reactor may include those reactors, can continuously supply ingredient and it can be continuously from wherein removing Remove product.The example of continuous mixing reactor includes twin-screw or multi-screw extruder (such as ring extruder).For even The method and apparatus of continuous preparation thermoplastic vulcanizates are described in United States Patent (USP) No.4311628；4594390；5656693； 6147160；It in 6042260 and WO2004/009327A1, is incorporated herein by reference, is used although can also use The method of low shear rate.Temperature of the blend when it passes through each barrel area or position of flow reactor can be with Variation as known in the art.Specifically, the temperature in curing area can be controlled according to the half-life period of curing agent used Or manipulation.

It is formed by that TPV is for example squeezed out by post-processing and calendering is further processed into suitable backboard, wherein by TPV packet Material, pellet, the sufficiently heating such as item squeeze out and are pressed into the plate of expectation thickness to melt the thermoplasticity phase.Suitable for directly including Any additive (being explained in detail below) in the TPV can also or instead be added in this post-processing stage, such to add Adding agent includes UV stabilizer, fire retardant, colorant (such as white or black colorant) etc..It is used to form the preferred of backboard TPV shows one of performance that will be described below or a variety of.

Hardness according to the suitable TPV of some embodiments is 30 shore A-50 shore D.In these specific embodiment party In case, hardness can be greater than 55 shore A, preferably greater than or equal to 60,65,70,75 or 80 shore A.Such embodiment party Case can show advantageous working ability, especially form the suitable thin backboard based on TPV (such as with according to aforementioned each Those of the thickness of backboard based on TPV of kind embodiment).For example, having the TPV of the thickness according to such embodiment It can permit and be extruded into relatively stressless plate (that is, plate with low internal stress).Low internal stress is in PV mould in the backboard It can be important during the long-life of block, especially when through heated and/or wet practice condition, and/or be subjected to periodicity When temperature change (substituting round the clock with the four seasons).When the backboard has excessive internal stress (such as formed when by softer TPV When), it may perhaps rupture this with encapsulating material layering in PV module and module is caused to deteriorate or even fail.Although this The risk of a problem can be reduced by using thicker backboard, but this solution is unpractiaca, because it is bright The aobvious material cost for increasing PV module, and further increase the weight of those modules and (and transport therefore and/or be mounted to This), while undesirably reducing the flexibility of such module.In general, thinner TPV can be manufactured in the case where not broken Plate, and at the same time having still maintained enough flexibility, this is better.

Hardness is measured according to ISO 868, from there through being incorporated by.According to identical agreement under ISO 868, no With test device it is different there may be degree as a result, hardness should use device according to ISO 7619 regulation measurement (and According to pervious standard DIN 53505).

Suitable TPV additionally or instead can be 1-15mPa in the modulus of 100% elongation (" M100 "), more excellent Select 1-10mPa.In certain embodiments, M100 can be 1-6mPa.M100, which has been measured, to be maintained at 100% for TPV sample and stretches Power needed for long rate based on the cross-sectional area of non-stretched sample, and is suitable flexible instruction.Specifically, M100 is got over Low, the flexibility of TPV material is bigger.

M100 is measured according to ISO 37, has following change/explanation: about sample preparation, sample cut direction Plate should be formed perpendicular to the flow direction TPV, from cutting sample thereon；In addition, should use I type die head (ISO 37, with The die head C of ASTM D412 is identical) carry out the cutting of dumbbell shape sample.Although ISO 37 defines sample and adjusts at 23+/- 2 DEG C Minimum 3h is managed, it is preferred that conditioning is to continue 16h 23 DEG C (this is also test temperature).About test of elongation rate equipment therefor, It is preferred that the device is T10 tensometer (Alpha Technologies) or equivalent (such as Zwick Z2.5/TH1s) and stretches Long meter, floor push shield and fixture shield.In addition, ISO 37 defines the intermediate value that test result is regarded as at least three value To determine；For the purpose of this paper, which is preferably derived from 3 values, closest for the material with Shore A hardness 0.05MPa (for the material with shore D hardness closest to 0.01MPa, wherein hardness measures as previously described).

Rubber components

The rubber components of the rubber components of the TPV formulation preferably cross-linking (can vulcanize).After dynamic vulcanization, institute's shape At TPV (that is, by include the dynamic vulcanization TPV formulation processing formed) in rubber components be at least partly crosslinked, it is excellent It selects fully crosslinked.

Any rubber suitable for manufacturing TPV can be used for manufacturing the TPV of (and being present in) some embodiments of the invention In.Term " rubber " refers to the polymer of any natural or synthesis the body performance that demonstrates flexibility, arbitrarily herein can With use synonymous with " elastomer ".The rubber components may include the mixing of a kind of rubber or two kinds or more kinds of rubber Object.

The rubber components are preferably present in TPV with the amount of 10-45wt% (such as 15-40,20-35 or 25-30wt%) In formulation (and/or be present in and be formed by TPV), the total weight based on the TPV formulation or TPV, if applicable Words.It is desirable that range may include range from any lower limit to any upper limit.Alternatively, it is prepared based on the TPV Object or the polymer content being formed by TPV (such polymer content is made of rubber components and thermoplastic component) In terms of the wt% of total weight, the preferred amount of the rubber components is 40-75wt%, such as 45-70wt% or 50- 65wt%, wherein it is desirable that range may include range from any lower limit to any upper limit.

The non-limitative example of rubber includes the rubber of olefin-containing, butyl rubber, natural rubber, and styrene-butadiene is total Copolymer rubber, butadiene rubber, acrylic-nitrile rubber, halogenated rubber such as bromination and chlorination isobutene-isoprene copolymer rubber Glue, butadiene-styrene-vinyl pyridine rubber, polyurethane rubber, polyisoprene rubber, epichlorohydrin terpolymer rubber Glue, (co) polychloroprene rubber and its mixture.

In some embodiments, which includes the rubber of olefin-containing, such as ethylene-α-olefincopolymerrubber.The second Alkene-alpha-olefin rubber may include the alpha-olefin with 3-8 carbon atom, and the alpha-olefin is third in preferred embodiments Alkene.The ethene-alpha-olefin rubber may include at least 50wt%, and perhaps the ethylene of at least 55wt% or at least 60wt% spread out Raw unit, the unit based on the weight of ethene-alpha-olefin rubber, and surplus are alpha-olefin derived.Ethene-alpha-olefin rubber Glue such as ethylene-propylene rubber further describes in United States Patent (USP) No.5177147.

In preferred embodiments, which includes ethene-alpha-olefin-diene rubber.The ethene-alpha-olefin- Diene rubber may include the alpha-olefin with 3-8 carbon atom.In preferred embodiments, which is propylene, and The rubber is Ethylene-Propylene-Diene rubber (" EPDM ").It is preferred that the diene in the ethene-alpha-olefin-diene rubber is non-conjugated Diene.Suitable non-conjugated diene includes 5- ethylidene -2- norbornene (" ENB ")；Isosorbide-5-Nitrae-hexadiene；5- methylene -2- drop Bornylene；1,6- octadiene；5- methyl-1,4- hexadiene；3,7- dimethyl -1,6- octadienes；1,3- cyclopentadiene；Isosorbide-5-Nitrae-ring Hexadiene；Bicyclopentadiene (" DCPD ")；5- vinyl -2- norbornene (" VNB ")；Divinylbenzene；Or a combination thereof.? In some embodiments, the ethene-alpha-olefin-diene rubber include diene derived from unit, be derived from ENB, VNB or its Combination.In preferred embodiments, the basic list by derived from ethylene, propylene and ENB of the ethene-alpha-olefin diene rubber Member composition is made from it.

Ethene-alpha-olefin-the diene rubber may include the unit of 50-90wt% ethylene derivative, for example, 55-80 or The unit of 60-70wt% ethylene derivative, based on ethene-alpha-olefin-diene rubber weight, wherein it is desirable that range can To include the range from any lower limit to any upper limit.Ethene-alpha-olefin-the diene rubber can further include 0.1- The diene of 10wt% (such as 3-7 or 4-6wt%), based on ethene-alpha-olefin-diene rubber weight, wherein making us the phase The range of prestige may include the range from any lower limit to any upper limit.Ethene-alpha-olefin-diene rubber content of monomer Surplus will generally comprise the unit derived from alpha-olefin such as propylene.In addition, suitable rubber, including suitable ethylene-α-alkene Hydrocarbon-diene rubber can be (that is, other than content of monomer, they may include extending oil) of oily increment.

Useful ethene-alpha-olefin rubber and ethene-alpha-olefin-diene rubber includes the rubber of some trades mark, can be Trade (brand) name Vistalon^TM(ExxonMobil Chemical Co.；Texas Houston), Keltan^TM(DSM Copolymers), Nordel^TMIP (Dow), Nordel^TMMG (Dow), Royalene^TM(Lion Copolymer) and Buna^TM (Lanxess) commercially available under.

Thermoplastic component

The thermoplastic component of the TPV (and/or the TPV formulation) includes at least one olefin thermoplastic resin." alkene heat Plastic resin " can be the material of any non-" rubber " as described herein.For example, the thermoplastic resin can be by this field skill Art personnel are considered the polymer of thermoplastic properties or the blend of polymer, such as such polymer, work as and are exposed to Soften and return when cooled to room temperature its initial condition when hot.The olefin thermoplastic resin component may include a kind of or more Kind polyolefin, including polyolefin homopolymer and polyolefin copolymer.

In some embodiments, the thermoplastic component depositing in the TPV formulation (and/or being formed by TPV) Can be 10wt%-30wt%, such as 14-28 or 16-25wt% in amount, wherein the wt% be based on TPV formulation (and/ Or be formed by TPV, if applicable) total weight, and it is desirable that range may include taking office from any lower limit The range of what upper limit.Alternatively, in the total weight of the TPV formulation or the polymer content being formed by TPV In terms of wt%, the preferred amount of the thermoplastic component is 25-60wt%, such as 30-55 or 35-50wt%, wherein making us Desired range may include the range from any lower limit to any upper limit.

Illustrative thermoplastic resin can be prepared by monoolefine monomer comprising but be not limited to former with 2-7 carbon The monomer of son, such as ethylene, propylene, 1- butylene, isobutene, 1- amylene, 1- hexene, 1- octene, 3- Methyl-1-pentene, 4- first Base-1- amylene, 5- methyl-1-hexene, mixture and its copolymer.It is preferred that the olefin thermoplastic tree in being formed by TPV Rouge is that unvulcanized or noncrosslinking (that is, before dynamic vulcanization, when being present in TPV formulation, it is can not to vulcanize Or non-crosslinked).

In preferred embodiments, which includes polypropylene or is made from it.As used herein , term " polypropylene " broadly indicates any such polymer, it is considered " polypropylene " by those skilled in the art, and And homopolymer, impact and random copolymer including propylene.It is preferred that polypropylene used in TPV as described herein, which has, is higher than 110 DEG C fusing point and unit including at least propylene derived of 90wt%.The polypropylene can also include isotaxy, atactic Or syndiotactic sequence, and preferably include isotactic sequence.The polypropylene can only derived from propylene monomer (that is, only Only with the unit of propylene derived) perhaps comprising at least 90wt% perhaps at least 93wt% or at least 95wt%, Huo Zhezhi Lack 97wt%, perhaps the unit of the propylene derived of at least 98wt% or at least 99wt%, and remaining is derived from alkene example Such as ethylene and/or C₄-C₁₀Alpha-olefin.

The melting temperature of the thermoplastic resin can be at least 110 DEG C, and perhaps at least 120 DEG C or at least 130 DEG C, and It can be 110 DEG C -170 DEG C or higher, be through DSC, as described in the 20th column 35-53 row of United States Patent (USP) No.6342565 Come what is measured, it is incorporated herein by reference.

The other components of TPV

TPV (and manufacturing TPV formulation used in the TPV) can further include oil, including processing oil (is added to TPV In formulation) and/or extending oil (it can reside in rubber components included by TPV formulation).The oil packet that can be used Include hydrocarbon ils and plasticizer, such as organic ester and synthesis plasticizer.Many additive-treated oils derive from petroleum distillate, and have specific ASTM title, this depends on whether they fall into alkane, in the classification of cycloalkane or aromatic naphtha.Other kinds of additive Oil includes alhpa olefin synthetic oil, such as liquid polybutene.Also the additive-treated oil for being different from the oil based on petroleum can be used, such as From the oil and synthetic oil of coal tar and pine tar, such as polyolefine material.In a particular embodiment, based on API points Group selects in the TPV included oil (such as API Group I, Group II, Group III, Group IV or Group V base stock Oil may be used as the oil in the TPV).In a particular embodiment, oil included in the TPV includes Group II or more advanced Oil, such as Group II oil (such as ParaLux^TM6001R technical oil, available from Chevron Texaco Corp.).Additionally Or instead, the oil may include white oil (such as pharmacy grade oil, such as Primol^TM542 medical grade white oils, available from The ExxonMobil Chemical Company of Texas Baytown).It is preferred that the oil is substantially colourless.? In certain embodiments, at least 90wt%, preferably 95wt% in the TPV, the oil of more preferable 99wt% is essentially colorless.Oil Color can according to ASTM D1500 determine；It is preferred that the color value of " essentially colorless " oil measured under this grade is less than 0.5, it is based on ASTM D1500 color grade.Using the ASTM D156 of Saybolt color grade particularly suitable for refining, intimate nothing The oil of color；Therefore, the preferred Saybolt color value of " essentially colorless " oil is+20 to+30, is measured by ASTM D156 's.

Amount of the oil in the TPV can be about 300 parts of about 5- perhaps 30-250 parts or 70-200 parts weights Amount, the total weight of rubber components and thermoplastic component based on 100 parts by weight, wherein it is desirable that range may include from appoint Range of what lower limit to any upper limit.In other words, in some embodiments, amount of the oil in the TPV can be from low To about 10wt% perhaps 15wt% perhaps 20wt% perhaps 25wt% perhaps 30wt% to height to about 40wt% or 45wt% perhaps 50wt% or 55wt%, the total weight based on the TPV, wherein it is desirable that range may include from appointing What lower limit is to any upper limit.

The TPV formulation further includes vulcanizing agent, can at least partly be disappeared during the dynamic vulcanization of TPV formulation Consumption.Can be used can solidify or be crosslinked any vulcanizing agent for preparing rubber used in the TPV.For example, including alkene in the rubber In the case where olefin elastomer copolymer, curing agent may include peroxide, phenolic resin, free radical curing agent, or routine Other curing agent used.In some embodiments, which includes phenolic resin.Curing accelerator (such as metal halogen Compound such as stannous chloride) it can be used for together with vulcanizing agent in the TPV formulation.Particularly useful vulcanizing agent, including phenols Resin and curing accelerator, including stannous chloride describe the PCT application No.PCT/US15/ submitted on December 10th, 2015 65048 [0046]-[0054] section, the description are incorporated herein by reference.

The TPV formulation can also include one or more additives, including metal oxide, acid scavenger, enhancing and Non-reinforcing fillers and/or incremental agent, antioxidant, stabilizer, antiblocking agent, antistatic agent, wax, foaming agent, pigment, fire retardant With any other additive, such as processing aid known to rubber compounding art.Useful filler and incremental agent includes conventional nothing Machine object such as calcium carbonate, clay, silica, talcum, titanium dioxide, carbon black and organic and inorganic nano-filler.Suitably [0055]-[0061] section for the international application No.PCT/US15/65048 that additive description was submitted on December 10th, 2015, Its description is incorporated herein by reference.

In some embodiments, particularly useful additive includes following one or more: UV stabilizer, UV inhibit Agent, antioxidant and fire retardant, any of which or a variety of can be PV module backplane that the TPV to be placed in one using institute It is desired.Useful fire retardant description discloses in No.WO2012/030577 [0043]-[0048] section in WIPO, and the description is logical It crosses and is incorporated herein by reference.Useful UV stabilizer includes the UV inhibitor containing phenol, UV stabilizer and antioxidant and hindered amine Light stabilizer.Carbon black can serve as black colorant, can also provide useful UV stability.

However, the TPV can there is no one of following or a variety of in still other embodiments: fire retardant, UV stabilizer, UV inhibitor and antioxidant, do not include carbon black." there is no " refers to being not present in this context Greater than the additive of negligible quantity.In a particular embodiment, any one or more of described additive depositing in TPV It is not more than 0.1wt%, preferably no greater than 0.05wt%, the weight based on the TPV in amount.In a particular embodiment, the TPV packet Containing being not more than 0.1, the preferably no greater than fire retardant of 0.05wt%.In still another embodiment, which additionally or instead wraps Containing the UV stabilizer total, preferably no greater than 0.05wt% total no more than 0.1wt%, UV inhibitor and antioxidant, no Including carbon black.

In addition, include white color agents, such as colored clay according to the desired TPV additive of still another embodiment, two Titanium oxide (it can also show useful anti-flammability), or suitable for assigning the TPV with other compounds of white, can have Increase the reflectivity of the electromagnetic energy of contact backboard sharply.It is at least partly transparent embodiment in the wherein post package material This can be it is particularly useful so that (such as light) is at least partly reflect returns to PV around any EM radiation of the PV battery Battery is used for potential collection and is converted to electric energy.

The additive of another potentially useful type includes functionalized polymeric, such as the polyethylene (PE- of maleic anhydride grafting ) or polypropylene (PP-g-MA) g-MA.The preferred functionalized polymeric that can be used is described in WO03/025084, WO03/ In 025037, WO03/025036 and EP patent No.1295926, whole is incorporated herein by reference.Such functionalized poly Closing object will be present in the thermoplasticity phase of TPV, and improve in some embodiments strong by the bonding of the TPV backboard formed It spends (such as laminated with encapsulating material to improve).

The formation of PV module

In some respects, present disclosure also relates to PV module is formed according to aforementioned modules.

PV module can be formed by conventional method, be wherein somebody's turn to do the backboard based on TPV and advantageously substituted Normal back plate.Cause This, in some embodiments, being formed includes the stacked body for heating (annealing) PV module layer.It is preferred that as shown in Figure 1, the layer Including at least preceding encapsulating material layer 105,110 array of PV battery, post package material layer 115 and backboard 120.The layer is with Fig. 1 Shown order arrangement, so that preceding encapsulating material layer 105 and post package material layer 115 sandwich PV cell array 110 wherein, And the post package material layer 115 is further adjacent with backboard 120, and contacts.According to Fig. 1, it optionally includes Foreboard 101 adjacent with preceding encapsulating material layer 105, and contacting.

Aforementioned layers preferably stack (that is, so that foreboard 101 is in bottom and backboard 120 is in top) in reverse order With heating (such as in autoclave).It is preferred that the front and rear encapsulating material layer 105 and 115 includes crosslinkable polymer material, and And the heating is in this way, that is, so that the encapsulating material is flowed and is crosslinked around PV battery (one or more), adheres to foreboard 101, battery 110 and backboard 120.Suitable heating temperature can change according to the characteristic of encapsulating material, but in some realities It applies in scheme, PV module layer stacked body is preferably heated to 90 DEG C -250 DEG C, such as 150 DEG C -250 DEG C, such as 150 DEG C -200 DEG C Temperature, and desired range includes any lower limit to any upper limit.

In other embodiments, which can stack that (such as backboard 120 is in bottom and foreboard from top to bottom 101 be in top) or edge-to-edge arrange (such as backboard 120 is at one end with foreboard 101 in other end), as long as the layer with Following order is arranged just: the preceding encapsulating material layer of foreboard-- PV cell array-post package material layer-backboard.

In the embodiment that the backboard wherein based on TPV is multilayer materials (for example including encapsulating material layer), letter The post package material layer 115 in foregoing description singly is omitted, comes so that multilayer materials backboard contacts in forming process PV cell array 110.

Equally, it is present in the embodiment of the either side of the backboard based on TPV in wherein one or more other layers In, before heating, such layer can be accordingly included the PV module layer heap before backboard (on its top) and/or later In stack.

It no matter include which kind of layer may be used also in some embodiments before or after heating PV module layer stacked body The side of stacked body is covered to include side frame (and optional sealant), if Fig. 1 is for shown in side frame 130 and sealant 131 Arrangement.Before side frame 130 and/or sealant 131 assemble, for PV battery 110 to be electrically connected to external charge carrying device Electric wire or other conductor wires (such as terminal box 111 or other electric installations) can further with PV battery (one or It is multiple) connection.It is further noted that PV battery (one or more) (such as is electrically connected by the description for completing PV component It is connected to external charge conduction device and any other structural support is provided) it is to come as the simple example in many examples It provides.The completion of component comprising aforementioned PV module layer stacked body usually can be by any means known in the art come complete At.

In some embodiments, which does not suffer from crosslinking substantially during component heating stepses.In order to determine Whether " there is no crosslinking " in TPV heating process, the first sample of the TPV can be first subjected to described previously herein Boiling xylene test；The second sample of the TPV can be subjected to heating condition identical with stack assemblies, be then subjected to boil Dimethylbenzene tests (according to program identical with for testing the first sample of TPV).If between the first and second TPV samples The difference (wt%) of extractable rubber in boiling xylene is less than 1wt%, then can be referred to as in the TPV heating process basic It is upper there is no crosslinking.

Advantageously, such formation produces such PV module, is not needing between encapsulating material and backboard wherein Adhesive layer.Instead, the backboard formed by the TPV according to foregoing description is preferably directly adhered on the encapsulating material, is not necessarily to Binder.

In some preferred embodiments, which carries out before above-mentioned stratification forms PV module with heating Sided corona treatment.The combinable surface area of TPV backboard can be increased according to the sided corona treatment of some embodiments, this is in backboard and envelope Sufficiently strong combination is produced between package material (also advantageously, so that the TPV backboard is at least partly directly adhered to Encapsulating material, that is, other binder material or layer are not necessarily between TPV backboard and encapsulating material).According to these implementations Some sided corona treatments of scheme can be carried out by any of means suitable for plastic surface.It generally includes to accelerate Electronics is to the frosting (being TPV here).This electron bombardment eliminates surface impurity, and also causes along the surface TPV At least some polymer chain scissions, this generates open ends and free valency.Meanwhile it can be produced during generating electron bombardment Raw ozone.The polymer chain reaction of the air and fracture of ozone and/or surrounding is generated along the surface molecular of the TPV containing oxidation Object is closed, can be more easily integrated in other surfaces.In general, only the surface molecular of TPV is by such sided corona treatment Influence (such as the TPV at the top of 0.00001 micron).

Alternatively, other surfaces are modified (such as is modified the surface molecular of the TPV to increase the place of the surface tension of TPV Reason), such as corona treatment can replace such sided corona treatment or is used together with such sided corona treatment.Therefore, In some embodiments, carried out with other PV module layers stratification and heating before, by based on TPV back plate surface processing come Improve its adhesiveness.

During heating the PV module layer stacked body, encapsulating material can undergo cross-linking reaction.Although such anti- Answer generally desired, but they can produce undesirable by-product, can weaken the globality of PV module, such as preceding institute It states.Equally, according to foregoing description, these by-products advantageously can permit according to the backboard based on TPV of some embodiments One of or it is a variety of escaped from inside modules, such as escaped by diffusing through this based on the backboard of TPV.Therefore, according to The PV module forming method of some embodiments includes generating one or more such cross-linking by-products during heating, with At least part of one or more by-products is made to pass through the PV module that backboard escapes the assembling afterwards.

It is desirable that PV module performance

As previously mentioned, including advantageously showing to improve according to the PV module of the backboard based on TPV of various embodiments Flexibility (due to flexibility of the aforementioned improved of the backboard based on TPV), reduced manufacturing cost, and bigger durability. Meanwhile such module additionally advantageously keeps or improves respective performances compared with conventional PV module performance.

For example, according to the admissible system voltage of maximum of the PV module of some embodiments can be 1000VDC or It bigger (preferably 1030VDC is perhaps bigger) while including that (such as back plate thickness is for average thickness 0.35mm or smaller backboard 0.10-0.35mm or 0.25-0.35mm).In such embodiments, maximum admissible system voltage can be 1000VDC-1500VDC, such as 1000-1200VDC or 1030-1200VDC, wherein it is also contemplated that being limited to from any The range of any lower limit.Maximum admissible system voltage is the instruction of the electrical insulation capability of the backboard based on TPV.Specifically, Maximum admissible system voltage has indicated the maximum voltage that can be observed safely in PV module, without being based on across insulation The backboard of TPV and the obvious risk for entering the uncontrolled electric discharge around PV module.Higher maximum permissible system voltage (that is, preferable backboard electrical isolation capabilities) illustrates a possibility that more effective PV operation (such as based on being exposed to incoming electromagnetic spoke The PV module front surface of every square metre penetrated, obtains the ability of more energy).

In addition, (being removed after being exposed to wet heat condition (85 DEG C/85% relative humidity) 3000h according to the agreement of IEC 61215 Exposure condition is 3000h, rather than 1000h described in current 61215 standard of IEC), according to the PV mould of some embodiments Block can additionally or instead show the PV block coupled in series resistance in illuminance (one-sun illumination) on the 1st (Rs) the smallest variation.Specifically, the variation of Rs in some embodiments can be less than or equal to 5%, preferably smaller than or Person is equal to 4% or even 3%.The higher increase of Rs may indicate that electric contact and/or mechanical failure in corrosion PV module should Battery itself, and/or swelling encapsulating material and/or other failures, cause higher at certain points in the circuit in PV module Resistance.Therefore, the increase of Rs is smaller in PV module operating process, and (being simulated by damp heat exposure) is better.

Additionally or instead, it can be shown in D-H process-exposed according to the PV module of some embodiments most The minimum change (Pmpp) that modular power exports at high-power point.It is preferred that being exposed to damp and hot item according to 61215 agreement of IEC After part (85 DEG C/85% relative humidity) 3000h, such PV module of some embodiments show Pmpp variation be greater than- 5% (that is, Δ Pmpp > -5%), preferably greater than -4% or even -3%.As used in context, change " being greater than " institute The negative value of record includes that the positive value of Pmpp changes the loss of (that is, Δ Pmpp > 0%) and Pmpp of the absolute value less than 5% (that is, Δ Both Pmpp>-5% and<0%).

Embodiment

Embodiment 1

Have rated the effect that sided corona treatment is carried out on the backboard that TPV is formed.Firstly, by Santoprene^TMThermoplasticity sulphur Change rubber 251-70W232 (the commercially available ExxonMobil Chemical Company obtained from Houston, Texas, United States) It is shaped to the plate of three 1.8cm (width) x 20cm (height), thickness is about 0.23mm.By three plates (sample S1, S2 and S3) 0,1 and 4 minute traveling time (this means that respectively sweep speed is 0,25 and 6.25cm/min) of sided corona treatment respectively.

In order to correctly test the adhesion strength of the backboard based on TPV, it is necessary to form multi-layer testing plate comprising two layers often Advising back veneer material, (Ref_BS is ICOSOLAR^TM2442,3-layer composite material (TEDLAR^TM/PET/TEDLAR^TM, in daylight Side is white, is black in opposite side), available from Austrian Isovoltaic AG.TEDLAR^TMIt is available from DuPont The PVF film and PET of Corporation is polyethylene terephthalate.Bigger rigid Normal back plate material allows with this The mode of sample carries out peel test force, will generate the controlled delamination of backboard and encapsulating material layer based on TPV；Otherwise, the base Applied stress will be responded in the backboard and encapsulating material of TPV and is easily deformed, this has distorted point for being based only upon peel strength The measurement of power necessary to layer.Therefore, adherency is tested, by the laminated multilayer knot at lower surface construction of each sample S1, S2 and S3 Structure: Ref_BS/EVA/TPV_BS/EVA/Ref_BS, wherein Ref_BS is just described, and TPV_BS is sample S1, S2 or S3 and EVA is conventional encapsulation materials (PHOTOCAP^TM15580P, it is commercially available obtained from Connecticut, USA Enfield's Specialized Technology Resources, Inc.).It is by adding lamellated plate in autoclave that five layers laminated together What heat was carried out to 160 DEG C.Keep 160 DEG C of temperature 10 minutes.After cooling, which is removed from autoclave.

Each multi-layer testing plate has carried out peel test in 22 DEG C of environment temperatures, with the detachment rate of 100mm/min.Record Each sample cause TPV and EVA to be layered needed for peeling force.Fig. 3 shows as sided corona treatment duration function, Standardized peeling force needed for layering (and the processing in 0 minute corresponding to sample S1 is taken as basic value " 1 ").Such as Fig. 3 institute Show, only 1 minute sided corona treatment (according to sample S2) increases the peeling force needed for being layered relative to untreated sample S1 About 40%, and 4 minutes sided corona treatments (according to sample S3) lead to be layered required peeling force relative to untreated sample Product S1 is increased just beyond 60%.With absolute value representation, the peeling force of sample S1 is 43.5+/- 3.0N/cm；The stripping of sample S2 It is 61.1+/- 4.5N/cm from power；Peeling force with sample S3 is that (given range is for illustrating reality by 70.0+/- 2.0N/cm Test standard deviation).

Embodiment 2

The backboard formed by five kinds of different materials is had studied under the conditions of different temperature, before damp and hot test and it The latter two, their adherency for EVA encapsulating material.The backboard for five seed types tested be the building material based on them come Label, as shown in table 1 below:

1. embodiment 2 of table is used to adhere to the backboard of test

ICOSOLAR^TM2442 be as described in front in embodiment 1.

SANTOPRENE^TMTPV251-70W 232 is a kind of fire-retardant, the color white trade mark thermoplastic vulcanizates, can Obtained from ExxonMobil Chemical Company, contain the EPDM for the crosslinking being dispersed in thermoplasticity (polypropylene) matrix Particle.Its hardness is that 75 shore A and M100 are 2.5MPa.

SANTOPRENE^TMTPV 101-55 is a kind of thermoplastic vulcanizates of trade mark, available from ExxonMobil Chemical Company contains the EPDM particle for the crosslinking being dispersed in thermoplasticity (polypropylene) matrix.Its hardness is 59 shore A and M100 are 2.1MPa.

SANTOPRENE^TMTPV 101-80 is a kind of thermoplastic vulcanizates of trade mark, available from ExxonMobil Chemical Company contains the EPDM particle for the crosslinking being dispersed in thermoplasticity (polypropylene) matrix.Its hardness is 86 shore A and M100 are 4.7MPa.

SANTOPRENE^TMTPV 251-80W232 is a kind of fire-retardant, the color white trade mark thermoplastic vulcanizates, Available from ExxonMobil Chemical Company, contain the crosslinking being dispersed in thermoplasticity (polypropylene) matrix EPDM particle.Its hardness is that 86 shore A and M100 are 3.8MPa.

Each of backboard aforementioned for five is prepared for similar to five layers of test board (ruler those of prepared by embodiment 1 Very little 1.8cm x 20cm).The test board each has structure: REF_BS/EVA/Test_BS/EVA/REF_BS, wherein Test_ BS is REF_BS or TPV_BS2-4, as described in Table 1.Such as the test board of embodiment 1, test board is formed in this way To assign the structure with enough rigidity, so that the power of layering is caused accurately to reflect peel strength (without result in required The flexible deformation of stratification forces).Each testing backboard sided corona treatment 4 minutes before being closed layer by layer with other test boards, and pass through It is heated at 160 DEG C and carries out within 10 minutes laminated forming five layers of test board.

Multiple each type of five layers of test boards are constructed, to evaluate each type of test under many different conditions Plate.Firstly, the peeling force (at Test_BS layers between EVA layer) for being layered each type of five layers of test board be at 23 DEG C, 40 DEG C, 60 DEG C, 85 DEG C and 100 DEG C each temperature measurings (that is, testing 25 test boards in total, each type of 1 is in Each temperature of 5 temperature conditions).As the result is shown in Fig. 4, although wherein it can be seen that REF_BS 23 DEG C have it is larger Peel strength (about 90N/cm, compared with the 65-70N/cm of TPV_BS1 and 4, and the 35-45N/cm phase with TPV_BS2 and 3 Than), the peel strength for the sample being all laminated on EVA encapsulating material is very similar at 60 DEG C, and at 85 DEG C and 100 It DEG C is almost indistinguishable (entirely 5-15N/cm).Internal temperature in the operation of PV module is usually 60 DEG C -80 DEG C, herein The adhesion strength for being all based on the backboard of TPV is similar to reference substance, this shows that TPV backboard as the whole of test realizes pair In the enough adherency of EVA encapsulating material, without binder.

Each of another group five layers of test board is each temperature survey at (23 DEG C, 40 DEG C, 60 DEG C, 85 DEG C and 100 DEG C) Examination, but carried out after damp and hot (D-H) of 1000h exposure.Damp heat exposure is according to damp and hot in 61215 characterization test of IEC What the agreement of test carried out, be incorporated herein by reference --- specifically, it is being suitable for humidity and temperature described in constant holding In 85% relative humidity and 85 DEG C of exposed 1000h in the phjytotron of condition.As the result is shown in Fig. 5.Fig. 5 shows similar The tendency of the adhesion strength test carried out before the D-H condition at 1000 hours, and REF_BS shows more preferably at 23 DEG C, It is behaved like with whole samples in 60 DEG C and higher temperature.However, after D-H exposure, with reference to backboard at 60 DEG C, 85 DEG C and 100 DEG C adhesion strength be lower than and (such as at 60 DEG C, do not have in same temperature without the adhesion strength of the plate of the same type of D-H exposure REF_BS needs about 28N/cm peeling force to be layered when having D-H exposure, but it is only necessary to about 20N/cm after D-H exposure Peeling force).On the other hand, influence of the D-H exposure for the backboard based on TPV obviously less it is significant (and at 60 DEG C, 85 DEG C and 100 DEG C of test time difference values are 0-4N/cm).This further highlights the backboard based on TPV and is being used for PV module reality with reference to backboard Similarity under the conditions of the occasion of border between adhesive property.

Finally, the D-H exposure in 2000h (also according to IEC 61215, replaces standard testing institute in addition to being exposed with 2000h It is required that 1000h) after, test and each of further organize five layers in each temperature (23 DEG C, 40 DEG C, 60 DEG C, 85 DEG C and 100 DEG C) Test board.

As the result is shown in Fig. 6.As 1000h D-H test as a result, 2000h D-H exposure after, whole bases Similar caking property is shown in common PV battery operational temperatures range (60-80 DEG C) with reference to backboard in the backboard of TPV.So And the bonding test after the D-H of 2000h exposure shows some surprising tendencies.Specifically, although most of plate Adhesion strength decline (compared with the D-H of the 0 and 1000h exposure) after the D-H exposure of 2000h is shown, still, with 1000h's D-H exposure is compared, TPV_BS2 and TPV_BS3 test board actually shows to increase after the D-H exposure of 2000h at 23 DEG C Adhesion strength.

In addition, it has been observed that the tensile strength of REF_BS is obviously reduced after the D-H exposure of 2000h, this to remove Test is difficult to carry out.On the other hand, TPV_BS sample does not show the obvious deterioration of mechanical strength advantageously, including stretches strong Degree.

In short, it is described test show the backboard based on TPV provide with the comparable adhesion strength of existing backboard, mention simultaneously The flexibility obviously increased is supplied.

Embodiment 3

6 mini PV module (20cm x 40cm) has been made, 2 concatenated PV battery (Sunways mono are each contained C-Si solar battery), and it is upper with uniform aluminium muddle layer on rear side of battery, and the battery of the coating further encapsulates In EVA (PHOTOCAP^TMIn 15580P), there is glass front plate (solar energy grade float glass, 3mm are thick).Each sample is mini The back veneer material of module is shown in the following table 2.The module is made by heating laminated 10 minutes at 160 DEG C.

The mini PV module backplane of 2. embodiment of table 3

Sample number into spectrum	Back veneer material	Back plate thickness
			PV1	SANtopRENETMTPV251-70W232	0.23mm
PV2	SANtopRENETMTPV101-55	0.30mm
			PV3	SANtopRENETMTPV101-80	0.29mm
PV4	SANtopRENETMTPV251-80W232	0.28mm
			PV5	ICOSOLARTM2442 (black sides towards sun side)	0.36mm
PV6	ICOSOLARTM2442 (white faces towards sun side)	0.34mm

It, will according to 61215 agreement of IEC (in addition to as mentioned, the 1000h of the protocol requirement is replaced using 3000h exposure) All 6 mini modules in the controlled environment chamber in be exposed to D-H condition 3000h.

Embodiment 3-1

It is visually inspected to evaluate the degree (if any) that layering and/or backboard are shunk in damp and hot research process. As a result it is recorded in the following table 3.

The mini PV module of visual inspection embodiment 3 after table 3. is damp and hot

Sample number into spectrum	Layering/mechanical failure	Backboard is shunk
			PV1	Nothing	It is very slight
PV2	Mechanical failure after 2000h (back side of plate is torn apart)	It is very slight
			PV3	Nothing	It is very slight
PV4	Nothing	It is very slight
			PV5	Nothing	Nothing
PV6	Nothing	Nothing

Very slight contraction is that about 240h is formed in D-H condition, and height arrives ruler when 3000h is marked in PV1-4 Very little not further change, this shows that contraction is small and is contained.The contraction does not show to influence PV performance.

After 1000h is damp and hot, IEC 61215 requires the PV module successfully tested to show not big visual deficiencies, As defined in the 7th article of IEC 61215.7th article includes following visual deficiencies: (a) being broken, the appearance of cracking or tearing Face, including cladding plate, substrate, frame and terminal box；(b) outer surface of bending or deflection, including cladding plate, substrate, frame and connect Wire box arrives such degree, that is, the installation and/or operation of module will be compromised；(c) crackle in battery, propagation will be from The cell area greater than 10% is removed in the circuit of module；(d) bubble or layering, in any part and mould of circuit Continuous path is formed between block edge；With euro loss of mechanical integrity, such degree, the i.e. installation of module and/or behaviour are arrived Work will be compromised.

The mini PV module all tested has passed through the visual inspection of IEC 61215.

However, PV2's is subject to mechanical failure after the D-H test of 2000h based on the backboard of TPV.This may be attributed to It is used to form the TPV and other (75-86 shore A) relatively low hardness (59 shore A) of this backboard, this demonstrate use foot The TPV of hardness is reached to form the thin importance for extending PV module life based on the backboard of TPV.

Additionally, it was found that some Huangs of EVA encapsulating material have occurred in the D-H process-exposed of the 3000h of sample P V1-4 Become.This xanthochromia is not considered as big visual deficiencies in IEC 61215.

Embodiment 3-2

It is also tested for electrical property of each mini PV module during damp heat exposure.Each PV module has been monitored entire Three kinds of performances during 3000h damp heat exposure: Pmpp (is exported) in the modular power of maximum power point, Isc (module short circuit electricity Stream) and Rs (series resistance of module in illuminance on the 1st).Have recorded each value at any time percentage variation (that is, so that It obtains in time t=0,0%) each value Δ Pmpp, Δ Isc and Δ Rs are.Less than 5% in the DH process-exposed of 1000h It is the successful test at IEC 61215 that Pmpp, which reduces (that is, Δ Pmpp > -5%),.Isc is when the voltage across battery is 0 (that is, when battery short circuit), across the electric current of PV battery.This represent the electricity of the theoretical maximum obtained by the solar battery Stream；The higher the better for value (that is, Isc reduction is undesirable) --- therefore, reduction as small as possible is sought for this value.It is another Aspect, the increase of Rs are undesirable, because this tends to the corrosion of electric contact in expression PV module --- therefore, for this Value seeks increase as small as possible.

It is every that Fig. 7-10 respectively illustrates PV1-4 (that is, 4 mini modules of PV with the backboard based on TPV according to table 2) A Δ Pmpp, Δ Isc and Δ Rs.As shown therein, each have the PV module of the backboard based on TPV not only in 1000h D-H exposure after passed through IEC61215；They have also passed through the test after 3000h.It is also noted that:, can be in Fig. 9 See that the Rs of PV3 increases after 1000h, but be to maintain it is highly stable, only+1.8% from 1500h to 3000h.This is significantly different In each others PV, wherein Rs shows the tendency upward in 3000h label.

Figure 11 and 12 shows PV5 and PV6 is identical value, with shown in table 2 refer to backboard.Although the two exists All pass through IEC 61215 after 1000h is damp and hot, but PV6 ultimate failure, it is shown that Pmpp's gradually decreases, sudden and violent in 3000h Reach -6.9% at the end of dew.Certainly, the Rs of PV6 is obviously increased in individual first 1000h test and (is reached+14%), so Further stable at the end of 3000h is tested afterwards to be deteriorated to+28%, this shows the obvious corrosion for electric line, and (it may return Because in Pmpp 3000h ultimate failure).In addition, PV5 shows substantially uniform Pmpp and Rs, until 2000h, in the point When, Pmpp starts to stablize decline, and in last individually 1000h test from 0% to -1.5%, and Rs is sharply increased, last single From+0.4% to+6.9% when only 1000h test.It is good that these tendencies show that the Normal back plate of PV5 is showed when starting, still Since the acceleration of Pmpp declines and it is easy to be influenced by the short life phase.

In short, the following table 4 also shows each mini PV module (rear panel module PV1-PV4 and Normal back plate based on TPV Module PV5 and PV6) Δ Pmpp after 3000h is damp and hot, Δ Isc and Δ Rs value.

Electrical property of the table 4. after the D-H exposure of 3000h

Sample number into spectrum	ΔPmpp	ΔIsc	ΔRs
				PV1	- 2.1%	- 1.5%	+ 2.4%
PV2	- 1.8%	+ 0.3%	+ 3.5%
				PV3	- 1.5%	- 0.1%	+ 1.8%
PV4	- 2.9%	- 1.2%	+ 4.7%
				PV5	- 1.5%	+ 0.5%	+ 6.9%
PV6	- 6.9%	- 1.5%	+ 28.0%

Embodiment 3-3

Also 0h, 1000h, 2000h and 3000h damp heat exposure with each mini module of 2 battery PV of image recording Electroluminescent (EL), and be respectively displayed in Figure 13-18.

Figure 13 shows that the EL of PV1 does not have significant change, and (its module electrical property only exists micro- with embodiment 3-2 for this Small deterioration) result it is consistent.

Figure 14 is shown during 500-3000h, and 2 dim spots are gradually formed in the upper cell of PV2, this may return Because of the corrosion of the aluminium paste of the breakdown (and last rupture) or cell backside in backboard.

Figure 15, which is shown, forms a small amount of filaments of sun in the upper part of PV3 top battery.It can also be seen that in top left side Crackle occurs in glass front plate during module making.Likely the crackle leads to the local losses of EL, and may Also already lead to PV3 corrosion shown in increased Rs after 1000h.

Figure 16 shows that the EL of PV4 does not have significant change after 1000h, and from 2000-3000h at the bottom of top battery Some small dim spots are formed in part, this is consistent with the deterioration of table 4 and the Rs of PV4 shown in Fig. 10.

Figure 17 similarly shows that the EL of PV5 does not have significant change after 1000h, but thereafter in the bottom of top battery Dim spot is formd on left side, this is consistent with the deterioration of the Rs of PV5 shown in table 4 and Figure 11.

Figure 18 shows on two batteries obvious dimmed, shows during the whole test, PV6 significantly smaller EL.This It is consistent with obviously increasing for the Rs of PV6 shown in table 4 and Figure 12.However, the image of Figure 18 shows that the loss of EL can be with attribution The corrosion that Al is pasted at cell backside, rather than moisture enters through the backboard, because the latter will usually show battery edge week It encloses dimmed, is gradually diffused into battery center (such as due to moisture from edge be gradually diffused into battery center).On the other hand, because It is identical paste for (and each module is subjected to identical condition) in each PV module, but it is to be noted that is based on The backboard of TPV does not show paste corrosion apparent in this way and degradation usually.That is, the reason of regardless of performance deterioration, survey Unique variable (in addition to glass crack accidental in above-mentioned PV3) is the class of backboard used in each module in die trial block Type.

Embodiment 4

The backboard of five different-thickness has been made, and has carried out electric discharge (PD) test of part.Partial discharge refers to Partial dielectric punctures in backboard, and it does not have the space between two conductors of bridging.It is desirable that backboard provides electrical isolation, With therefore should show as the high as possible admissible system voltage of maximum, without allowing any part across backboard to put Electricity.

PD test is carried out according to EN 61730:2007.U_i(starting voltage of partial discharge) and U_e(partial discharge Extinction voltage) measurement method it is as follows: increase to voltage U first_i, then wait 5 seconds and further increase other 10%, then It waits other 5 seconds.Then, U is reduced the voltage to_e, and voltage decreasing rate is 20V/s.U_eIt must be that 60s free portion is put Electricity.If PD intensity descends below 1pC within 60 seconds time, it is considered having reached extinction voltage.

PD intensity be according to IEC 60243-1 (measurement solid insulating material electric strength standardized test), pass through by Each of 10 samples of each type of backboard is continuously placed between two test electrodes (25mm/75mm diameter) and evaluates 's.Impedance is measured in the ground side of test sample.For the Insulation Coordination of test device, according to standard IEC 60664-1:2007.The test is that (temperature changes in entire test process, in such case in 37% relative humidity and room temperature In be 21 DEG C -24.5 DEG C) carry out.

For each sample backboard, 10 each extinction voltage (10 samples of each type backboard of test are had recorded Each of on 1), and calculate the average extinction voltage and experimental standard deviation of each type of sample.In addition, each back Admissible system voltage (the U of maximum of plate_max) it is to be measured based on IEC 60664-1: U_max=U_e x 1.414/(1.2x 1.25), wherein for each sample type, U_eIt is to subtract experimental standard deviation with average extinction voltage calculated come really Fixed, 1.414 be the calculated value of the system peak voltage, 1.2 expression factors of safety (consider environmental condition such as humidity and The variation of temperature) and 1.25 indicate other factor of safety (insulation according to IEC 60664-1 for reinforcing).

Finally, it is noted that extinction voltage (and therefore maximum admissible system voltage) depends on the thickness of backboard. Therefore, the average thickness of each backboard is by the thickness and each sample four at measurement each rectangular back plate sample center The thickness at each place at a turning determines.The average value of five thickness measurements is taken as average thickness.The following table 5 lists institute The each average extinction voltage of five kinds of backboard types of test, maximum admissible system voltage and thickness.

5. partial discharge test result of table

Back veneer material	Average thickness	Ue(average)	Experimental standard deviation	Umax
					ICOSOLARTM2442	0.360mm	1133V	75V	997VDC
SANtopRENETMTPV101-55	0.299mm	1167V	67V	1037VDC
					SANtopRENETMTPV101-80	0.994mm	2368V	59V	2176VDC
SANtopRENETMTPV251-80W232	0.559mm	1764V	145V	1526VDC
					SANtopRENETMTPV101-80	0.287mm	1177V	84V	1031VDC

Interestingly, although being 0.360mm thickness with reference to ICOSOLAR plate, it show than by SANTOPRENE^TMThe slightly lower admissible voltage of maximum of even more thin backboard made of TPV 101-80 and 101-55, this table The obvious benefit of the backboard electrical insulation capability based on TPV is shown, especially with a thickness of about 0.35mm or lower, or even It is even more so when 0.3mm or lower.

Although describe and illustrating the present invention by reference to specific embodiment, those of ordinary skill in the art will Understand, the present invention can take necessarily variation shown in this article.It for this reason, therefore should be referring only to appended power Sharp claim determines true scope of the invention.All files as described herein are incorporated herein by reference, including any excellent First weigh file and/or test program, if they not with contradict herein.Equally, term "comprising" is considered as and term " packet Include " it is synonymous.Work as composition, when having conjunction "comprising" before element or element group, it is thus understood that unless the context otherwise It is explicitly indicated, otherwise it is also contemplated that before the composition, the record of one or more elements " substantially with conjunction By ... form ", " by ... form ", the identical of " selected from by ... the group formed " either "Yes" form or element group, Vice versa.

Claims (17)

1. An articulated photovoltaic module, containing: A single backing plate comprising thermoplastic vulcanizate and having one or more hinge locations thereon; wherein the thermoplastic vulcanizate comprises at least partially vulcanized rubber dispersed in a continuous thermoplastic matrix; and a plurality of photovoltaic module assemblies arranged on one side of the backplane and spaced along the backplane such that there is a hinge space between each photovoltaic module assembly, each of the hinge spaces corresponding to the backplane the hinged position of the plate; wherein each photovoltaic module assembly includes one or more photovoltaic cells at least partially encapsulated in an encapsulation material, and the encapsulation material of each respective photovoltaic module assembly is in contact with a portion of the backsheet. 2. The hinged photovoltaic module of claim 1, wherein the backplane is configurable such that each hinge position independently defines an angle between adjacent photovoltaic module assemblies within a range of 0° to 360°. 3. The hinged photovoltaic module of claim 1 or claim 2, wherein the average thickness of the backsheet measured at each hinge location is at most 80% of the average thickness of the backsheet measured away from each hinge location. 4. The hinged photovoltaic module of any of the preceding claims, wherein the thermoplastic vulcanizate has a modulus (M100) at 100% elongation in the range of 1 to 10 MPa. 5. The hinged photovoltaic module of any preceding claim, wherein the thermoplastic vulcanizate has a hardness of at least 55 Shore A. 6. The hinged photovoltaic module of claim 5, wherein the thermoplastic vulcanizate has a hardness of at least 70 Shore A. 7. The hinged photovoltaic module of any preceding claim, wherein the encapsulant of each photovoltaic module assembly is adhered to in the absence of any adhesive between the backsheet of each photovoltaic module assembly and the encapsulant. backplane. 8. The hinged photovoltaic module of any preceding claim, wherein the thermoplastic vulcanizate has been subjected to corona treatment prior to adhering to said at least a portion of the encapsulant. 9. The hinged photovoltaic module of any preceding claim, wherein the backsheet has an average thickness in the range of 0.1 to 1.5 mm, the average thickness being measured at locations other than one or more hinge locations. 10. The hinged photovoltaic module of any preceding claim, wherein the backsheet consists of the thermoplastic vulcanizate. 11. The hinged photovoltaic module of any preceding claim, wherein the encapsulant of each photovoltaic module assembly comprises: (i) a front encapsulant coating the front side of each photovoltaic cell of each photovoltaic module assembly, and (ii) a back encapsulant coating the backside of each photovoltaic cell of each photovoltaic module assembly, and further a back encapsulant wherein the back sheet is adhered to at least a portion of each photovoltaic module assembly. 12. The hinged photovoltaic module of claim 11, wherein one or both of the front encapsulation material and the rear encapsulation material independently comprise a polymeric material selected from the group consisting of: ionomer, thermoplastic polyurethane (TPU), polyvinyl butyral Aldehyde (PVB), Polydimethylsiloxane (PDMS), Ethylene Vinyl Acetate (EVA) and combinations thereof. 13. The hinged photovoltaic module of any preceding claim, wherein each photovoltaic module assembly includes a side frame and a front panel. 14. The hinged photovoltaic module of any preceding claim, wherein less than 10 wt% of the at least partially vulcanized rubber is extractable from thermoplastic vulcanizate in boiling xylene. 15. The photovoltaic module of claim 14, wherein 0.1 to 2.0 wt% of the at least partially vulcanized rubber is extractable from thermoplastic vulcanizate in boiling xylene. 16. The photovoltaic module of any of the preceding claims, wherein the at least partially vulcanized rubber of the thermoplastic vulcanizate is an ethylene-propylene-diene (EPDM) rubber; and further wherein the continuous thermoplastic matrix comprises polypropylene. 17. The photovoltaic module of any preceding claim, wherein the thermoplastic vulcanizate comprises one or more of a UV stabilizer and a functionalized polymer.