TW201631789A - Solar cell module and method for producing solar cell module - Google Patents

Abstract

In the present invention, a solar cell module has a light-permeable substrate on a light-receiving surface side and a back surface protective material on a back-surface side, wherein the solar cell module has a structure such that EVA (ethylene vinyl acetate copolymer) and silicone are adjacent and layered as the sealant between the light-permeable substrate on the light-receiving surface side and a solar cell element, and such that the solar cell element and back surface protective material are sealed by the EVA. This solar cell module can be easily produced using a vacuum laminator without greatly modifying the solar cell production steps. A reduction in output of the solar cell module accompanying the PID phenomenon can be inhibited because the solar cell module has very strong resistance to the PID phenomenon.

Description

Solar battery module and solar battery module manufacturing method

The present invention relates to a solar cell module and a method of fabricating the same.

A crystal solar cell module in which a solar cell element comprising a semiconductor substrate made of a semiconductor substrate or the like is provided, and a light-transmitting substrate such as glass is provided on the photosensitive surface side, and a light-transmitting substrate such as glass is provided on the rearmost side. It is also an inner protective material such as a PET film, and EVA is widely used as a sealing material existing therebetween.

On the other hand, in recent years, many solar power generation systems having large-scale power generation capacity called large-scale solar power plants have been constructed. In such a solar power generation system having a large-scale power generation capacity, the voltage applied to each solar battery module sometimes becomes a high voltage, and the output of the solar battery module may be lowered due to the difference in the installed outdoor conditions. . This output reduction phenomenon is called PID (Potential Induced Degradation).

One of the reasons is that it is proposed that a high voltage is applied to the module monomer, so that the Na ⁺ component in the glass passes through the sealing material and reaches the surface of the solar cell unit, resulting in recombination of the surface of the solar cell unit, resulting in lower output. Etc. (Non-Patent Document 1).

The countermeasure for improving the problem is an improvement of the photosensitive surface antireflection film of the solar cell unit (Patent Document 1).

However, the improvement of the photosensitive surface anti-reflection film has a problem that the output of the solar cell unit is slightly lowered, or in the step of forming the anti-reflection film of the solar cell, it is necessary to improve the device.

Further, as a countermeasure against the solar power generation system, there is a method in which a current transformer element portion of the solar battery module is not used as a negative current using a current transformer with an insulating transformer. However, in order to increase the efficiency and cost of the converter, many transformerless converters have been introduced, and countermeasures based on system changes have become difficult.

The countermeasures to improve this problem are changes in sealing materials. The PID phenomenon is generally confirmed in the case of using EVA (Non-Patent Document 1). The sealing material having PID resistance includes an ionic compound, and the cost of the ionic compound is high, and there is a problem that the production cost of the solar cell module is increased.

Further, a solar battery module having a structure in which a laminate of an ionic compound and EVA is sealed has been proposed (Non-Patent Document 2). In this configuration, the ionic compound prevents Na ⁺ diffusion from the photosensitive glass and suppresses the generation of PID. However, when the ionic compound and the EVA are superposed by a vacuum laminator and heated and vacuum-molded, bubbles are likely to remain at the interface, and it is difficult to obtain a molded body favorably. As a countermeasure against this, a method of inserting a transparent PET resin film sheet between EVA and an ionic compound has been proposed (Patent Document 2).

In this method, it is necessary to laminate three layers of an ionic compound, a PET resin film, and EVA between the glass and the unit, and the steps are complicated.

Further, examples of the sealing material which does not cause a PID phenomenon include polyfluorene oxide. In the solar cell module using polyfluorene as a sealing material, it is proposed that the PID phenomenon is less likely to occur (Non-Patent Document 1).

However, in general, polyfluorene is a liquid, and in order to be introduced into the solar cell module, not only new equipment but also material cost is increased, and the manufacturing cost of the solar cell module is increased.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2014-11246

Patent Document 2: Japanese Laid-Open Patent Publication No. 2014-157874

Non-patent literature

Non-Patent Document 1: PVeye August issue (2012)

Non-Patent Document 2: P. Hacke, et. al "Characterization of Multicrystalline Silicone Modules with System Bias Voltage Applied in Damp Heat", 25 ^th European Photovoltaic Solar Energy Conference and Exhibition, Valensia, Spain, 2010

The present invention has been made to solve the above problems, and an object of the invention is to provide a solar cell module which is easy to carry out a solar cell module step, which is excellent in lamination sealing, and which is excellent in PID resistance and a method for manufacturing the same.

The present inventors have carefully studied the above-mentioned problems, and found that a laminate of EVA and polyoxyn oxide is used in a series of solar cell elements (a plurality of solar cell elements and a connection body connecting the solar cell elements) The sealer is valid.

That is, the present invention relates to the following solar cell module and a method of manufacturing the same.

[1] A solar cell module having a light transmissive substrate on a photosensitive surface side and a solar cell module having an inner surface protective material on an inner surface side, wherein: a photosensitive surface side light transmissive substrate and The sealing material between the solar cell elements is a structure in which EVA (ethylene-vinyl acetate copolymer) is laminated adjacent to the polyfluorene oxide, and the solar cell element and the inner surface protective material are sealed by EVA. The structure of the room.

[2] A solar cell module having a light-transmissive substrate on a photosensitive surface side and a solar cell module having an inner surface protective material on an inner surface side, wherein the photosensitive surface side light-transmitting substrate and The sealing material between the solar cell elements is a structure in which EVA (ethylene-vinyl acetate copolymer) is laminated adjacent to polyfluorene oxide, and is bonded to the inner surface protective material and the solar cell element. The structure in which EVA (ethylene-vinyl acetate copolymer) is laminated adjacent to polyoxymethylene.

[3] The solar cell module according to [1], wherein the EVA is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent polyoxygen is in contact with the solar cell element.

[4] The solar cell module according to [1], wherein the polyoxynium is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent EVA is in contact with the solar cell element.

[5] The solar cell module according to [2], wherein the EVA is in contact with the light-transmitting substrate on the photosensitive surface side and the inner surface protective material, respectively, and the adjacent polysilicon oxide is in contact with the structure of the solar cell element.

[6] The solar cell module according to [2], wherein the polyoxynium is in contact with the light-transmitting substrate on the photosensitive surface side and the inner surface protective material, and the adjacent EVAs are respectively in contact with the structure of the solar cell element.

[7] The solar cell module according to [2], wherein the EVA is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent polyfluorene is in contact with the photosensitive surface of the solar cell element, and the polyoxygen is in contact with The inner surface protection material, the adjacent EVA is in contact with the inner surface of the solar cell element.

[8] The solar cell module according to [2], wherein the polyoxygen is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent EVA is in contact with the photosensitive surface of the solar cell element, and the EVA is in contact with the inner surface. The protective material is in contact with the adjacent structure of the inner surface of the solar cell element.

[9] The solar cell module according to any one of [1] to [8] wherein the EVA and the polyoxygenated oxygen form a double layer structure in which EVA and polyfluorene are formed. The composite laminate has a thickness of 0.05 to 3 mm and a thickness of the composite laminate of 0.45 to 3.6 mm.

[10] The solar cell module according to any one of [1] to [9] wherein the polyfluorene oxygen is a hardened material comprising the polyoxonium oxide composition of the following (A) to (C),

(A) 100 parts by mass of an organopolyoxane having a polymerization degree of 100 or more as shown by the following average composition formula (I)

R ¹ _a SiO _(4-a ) _/2 (I)

(wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species, and a is a positive number of 1.95 to 2.05)

(B) 20 to 150 parts by mass of reinforcing cerium oxide having a specific surface area of 50 m ² /g or more

(C) Hardener An effective amount to harden the component (A).

[11] The solar cell module according to any one of [1] to [10] wherein the inner surface light transmissive substrate is used as the inner surface protective material.

[12] The method for manufacturing a solar cell module according to any one of [1] to [11] wherein the solar cell module has a light transmissive substrate on the side of the photosensitive surface, and the EVA is A laminate having a two-layer structure superposed on a polysulfide composition in an unsulfurized state is placed on a light-transmitting substrate, and a solar cell element is placed in series on the upper portion of the laminate, and is arranged in a solar cell element. On the back surface, a single layer of EVA or a laminate of EVA and an unsulfurized polyfluorene composition is laminated as a two-layer structure, and the inner protective material is laminated on the back side, and a vacuum laminator is used. Heating and pressing under vacuum to make unsulphurized The polyoxyl composition of the state and the EVA are crosslinked and thereby modularized.

The solar cell module of the present invention can be easily fabricated using a vacuum laminator without significantly changing it in the solar cell module manufacturing step, and has great resistance to the PID phenomenon, and can suppress the phenomenon accompanying the PID. The output of the solar cell module is reduced.

100, 200, 300, 400, 500, 600, 700, 800, 900, 1000‧‧‧ solar battery modules

101‧‧‧Light penetrating substrate

102‧‧‧Fitting material EVA

103‧‧‧Flaming material polyoxyl

104‧‧‧Solar battery components

105‧‧‧Inside protective materials

Fig. 1 is a cross-sectional view showing a solar battery module according to a first embodiment of the present invention.

Fig. 2 is a cross-sectional view showing a solar battery module according to a second embodiment of the present invention.

Fig. 3 is a cross-sectional view showing a solar battery module according to a third embodiment of the present invention.

Fig. 4 is a cross-sectional view showing a solar battery module of a fourth embodiment of the present invention.

Fig. 5 is a cross-sectional view showing a solar battery module according to a fifth embodiment of the present invention.

Figure 6 is a cross-sectional view showing a solar battery module of a sixth embodiment of the present invention.

Fig. 7 is a cross-sectional view showing the solar cell module of the first comparative example.

Fig. 8 is a cross-sectional view showing a solar battery module of a second comparative example.

Fig. 9 is a cross-sectional view showing a solar battery module of a third comparative example.

Fig. 10 is a cross-sectional view showing a solar battery module of a fourth comparative example.

The solar cell module of the present invention has a light transmissive substrate on the photosensitive surface side and an inner surface protective material on the inner surface side. Between the photosensitive surface and the inner surface, a plurality of solar cells are disposed. a device and a series of solar cell elements connecting the plurality of solar cell elements connected to each other, sealing the surface side sealant of the series, and being filled between the light transmissive substrate and the solar cell element series, The inner sealing material is filled between the inner surface protective material and the solar cell element series.

In this case, the solar cell element can be applied to a person composed of a P-type semiconductor substrate, a member made of an N-type semiconductor substrate, or a thin film device, and the effects can be exhibited in all of the above.

Further, as the light transmissive substrate, white plate glass, polycarbonate, acrylic plate or the like can be used. Here, the whiteboard glass is generally made of soda lime glass. Soda-lime glass is easy to produce Na ⁺ ions. When systemized, when a large number of solar modules are connected in series, when a high voltage (negative) load is generated on the unit side, Na ⁺ ions will move toward the unit side and reach the unit. The surface is recombined to cause a decrease in the output of the solar cell module. However, the present invention is highly resistant to the PID phenomenon, and can suppress the output of the solar cell module accompanying the PID phenomenon, so that it can be effectively used. Whiteboard glass.

The inner protective material is TPT "PVF (polyvinyl fluoride) / Adhesive / PET (polyethylene terephthalate) / adhesive / PVF) or TPE "PVF / adhesive / PET / adhesive / EVA", or especially "PVF / adhesive / PET" A film or the like of the laminate is shown. Further, as the inner surface protective material, the same light transmissive substrate as the above surface side may be used.

In the present invention, the surface side sealant is a composite laminate of EVA and polyfluorene. On the other hand, as the inner sealer, EVA alone or a composite laminate of EVA and polyoxymethylene which is the same as the front sealant may be used.

In this case, as the use form of the front side sealant, either EVA or polyfluorene oxide may be located on the side of the light-transmitting substrate, and in addition, when the above composite laminate is used as the inner surface protective material, EVA and polyfluorene Any of the oxygen may be located on the side of the inner protective material.

Fig. 1 to Fig. 6 show the arrangement of the sealant. In other words, in the solar cell module 100 according to the first embodiment of the present invention, the white glass as the light-transmitting substrate 101, the sealing material EVA102, and the polyoxyl oxide 103 are sequentially applied from the incident direction of sunlight. The crystal 矽 solar cell element series 104, the sealing material EVA 102, and the inner surface protective material 105 are formed. These laminates are heated and pressed under vacuum by a vacuum laminator, and crosslinked to form an integration. The solar cell module 100 thus formed is surrounded by an aluminum frame and connected to a grounded metal frame.

In the solar cell module 200 according to the second embodiment of the present invention, the white glass as the light-transmitting substrate 101, the sealing material polyoxyl 103, and the EVA 102 are sequentially applied from the direction of sunlight incident. The crystallization solar cell element series 104, the sealing material EVA 102, and the inner surface protective material 105 are formed.

In the solar cell module 300 according to the third embodiment of the present invention, the white glass as the light-transmitting substrate 101, the sealing material EVA102, the polyfluorene oxide 103, and the crystallization crystal are sequentially applied from the incident direction of the sunlight. The solar cell element series 104, the sealing material EVA 102, the polyoxane 103, and the inner surface protective material 105 are formed.

In the solar cell module 400 according to the fourth embodiment of the present invention, the white glass as the light-transmitting substrate 101, the sealing material, the polyoxygen oxide 103, the EVA 102, and the crystalline germanium are sequentially applied from the incident direction of the sunlight. The solar cell element series 104, the sealing material EVA 102, the polyoxane 103, and the inner surface protective material 105 are formed.

In the solar cell module 500 according to the fifth embodiment of the present invention, the white glass as the light-transmitting substrate 101, the sealing material EVA102, the polyfluorene oxide 103, and the crystallization crystal are sequentially applied from the incident direction of sunlight. The solar cell element series 104, the sealing material polyoxane 103, the EVA 102, and the inner surface protective material 105 are formed.

Fig. 6 is a view showing a solar cell module 600 according to a sixth embodiment of the present invention, in which a white glass as a light-transmitting substrate 101, a sealing material, a polyoxyl oxide 103, an EVA 102, and a crystal yttrium are sequentially applied from a direction in which sunlight is incident. The solar cell element series 104, the sealing material polyoxane 103, the EVA 102, and the inner surface protective material 105 are formed.

Here, in the composite laminate, the thickness of the polyfluorene oxide is 0.05 to 3 mm, particularly preferably 0.1 to 1 mm, and the thickness of the EVA is preferably 0.4 to 0.6mm. At this time, the thickness of the composite laminate is 0.45 to 3.6 mm, and particularly preferably 0.5 to 1.6 mm.

On the other hand, when only EVA is used as the inner sealant, the thickness is preferably 0.4 to 0.6 mm.

In the present invention, EVA (ethylene-vinyl acetate copolymer) can be used as a user in a solar cell module, and a commercially available product can be used. As a general product, ethylene and vinyl acetate are copolymerized at a mass ratio of 75:25 to 65:35, which is commercially available.

Further, in the present invention, polyfluorene oxide is preferably obtained by curing a polyfluorene oxide composition containing the following components (A) to (C).

(A) 100 parts by mass of an organopolyoxane having a polymerization degree of 100 or more as shown by the following average composition formula (I)

R ¹ _a SiO _(4-a)/2 (I)

(wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species, and a is a positive number of 1.95 to 2.05)

(B) 20 to 150 parts by mass of reinforcing cerium oxide having a specific surface area of 50 m ² /g or more

(C) hardener effective amount to harden component (A)

Specifically, the component (A) is an organopolysiloxane having a polymerization degree represented by the following average composition formula (I) of 100 or more.

R ¹ _a SiO _(4-a)/2 (I)

(wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species, and a is a positive number of 1.95 to 2.05)

In the above average composition formula (I), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species, and usually has a carbon number of 1 to 12, particularly preferably a carbon number of 1 to 8, and specifically, a methyl group is mentioned. An alkyl group such as an ethyl group, a propyl group, a butyl group, a hexyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; a cycloalkenyl group or a benzene group; An aryl group such as a benzyl group or a tolyl group; an aralkyl group such as a benzyl group or a 2-phenylethyl group; or a group in which a part or all of the hydrogen atoms of the group is substituted by a halogen atom or a cyano group or the like; It is a methyl group, a vinyl group, a phenyl group, or a trifluoropropyl group, and particularly preferably a methyl group or a vinyl group.

Specifically, it is preferred that the main chain of the organopolyoxane is composed of a repeat of a unit of dimethyloxane or a repeat of a unit of dimethyloxane constituting the main chain. a part of the structure of the dimethyl polyoxane, a diphenyl siloxane unit having a phenyl group, a vinyl group, a 3,3,3-trifluoropropyl group, or the like, a methylphenyl siloxane unit, A methyl vinyl siloxane unit, a methyl-3,3,3-trifluoropropyl decane unit, or the like.

In particular, the organic polyoxyalkylene is preferably an aliphatic unsaturated group having two or more alkenyl groups or cycloalkenyl groups in one molecule, and particularly preferably a vinyl group. In this case, 0.01 to 20 mol%, particularly preferably 0.02 to 10 mol%, of all R ¹ is an aliphatic unsaturated group. The aliphatic unsaturated group may be bonded to a ruthenium atom at the end of the molecular chain, or a ruthenium atom bonded to the middle of the molecular chain, or both, but is preferably a ruthenium atom bonded at least to the end of the molecular chain. Further, a is 1.95 to 2.05, preferably 1.98 to 2.02, and particularly preferably a positive number of 1.99 to 2.01.

The organopolyoxane of the component (A) is preferably exemplified by a trimethylphosphonium alkyl group, a dimethylphenylphosphonium group, a dimethylhydroxyphosphonyl group, or a methyl group. Blocked by a triorganophosphonyloxy group such as a vinyl oxiranyl group, a methyl divinyl decyl oxyalkyl group or a trivinyl decyl oxyalkyl group. Particularly preferred are methyl vinyl polyoxyalkylene, methylphenylvinyl polyoxyalkylene, methyltrifluoropropylvinylpolyoxyalkylene and the like.

The organopolyoxane can be subjected to (co)hydrolysis condensation of one or two or more kinds of organic halogen decane, or by using a basic or acidic catalyst to form a cyclic polyoxane (a siloxane). It is obtained by a trimer, a tetramer, or the like. These are substantially linear diorganopolyoxyalkylene oxides, but the component (A) may be a mixture of two or more kinds of molecular weights (degree of polymerization) or molecular structures.

The degree of polymerization of the above organopolyoxane is 100 or more, preferably 100 to 100,000, particularly preferably 3,000 to 20,000. The degree of polymerization can be measured as a polystyrene-equivalent weight average degree of polymerization by gel permeation chromatography (GPC: Gel Permeation Chromatography) analysis.

The reinforcing cerium oxide having a BET specific surface area of (B) of 50 m ² /g or more is added to obtain a composition excellent in mechanical strength before and after curing. At this time, in order to enhance the transparency of the polyoxyxene sealing material, the BET specific surface area is preferably more than 200 m ² /g, and more preferably 250 m ² /g or more. When the BET specific surface area is 200 m ² /g or less, the transparency of the cured product may be lowered. The upper limit is not particularly limited and is usually 500 m ² /g or less.

The reinforcing cerium oxide of the component (B) can be exemplified by smoke Ruthenium dioxide (dry cerium oxide or smoked cerium oxide), precipitated cerium oxide (wet cerium oxide), and the like. Further, it is also preferred to use a surface which is hydrophobized with chlorodecane, alkoxy decane or hexamethyldioxane. In particular, it is preferred because the treatment of hexamethyldioxane improves transparency. In order to improve transparency, it is preferred to use fumed cerium oxide as the reinforcing cerium oxide. The reinforced cerium oxide may be used singly or in combination of two or more.

A commercially available product can be used as the reinforcing cerium oxide of the component (B), and examples thereof include the Aerosil series (Nippon) such as Aerosil 130, Aerosil 200, Aerosil 300, Aerosil R-812, Aerosil R-972, and Aerosil R-974. Aerosil Co., Ltd.); Cabosil MS-5, MS-7 (manufactured by Cabot Corporation); Reolosil QS-102, 103, MT-10 (manufactured by Tokuyama Co., Ltd.), etc., surface untreated or surface hydrophobized ( Smoked cerium oxide, that is, hydrophilic or hydrophobic, or surface untreated or dried by Tokuseal US-F (manufactured by Tokuyama Co., Ltd.), NIPSIL-SS, NIPSIL-LP (manufactured by Nippon Silica Industrial Co., Ltd.) The surface is hydrophobized by sedimentation of cerium oxide or the like.

The amount of the reinforcing cerium oxide of the component (B) is 20 to 150 parts by mass, preferably 30 to 90 parts by mass, more preferably 50% by mass based on 100 parts by mass of the organopolysiloxane of the component (A). ~90 parts by mass. When the amount of the component (B) is too small, the reinforcing effect before and after curing cannot be obtained, and the transparency after curing of the polyoxygenated sealing material is lowered. When the amount is too large, the dispersion of cerium oxide into the polyoxygenated sealing material becomes difficult, and at the same time, the processability of processing into a sheet form is deteriorated.

The curing agent of the component (C) is not particularly limited as long as it can harden the component (A), and is preferably a (a) addition reaction (hydrogenated decane) which is a hardening agent of a well-known polyfluorene oxide composition. A type of hardener, that is, a combination of an organic hydrogen polyoxyalkylene (crosslinking agent) and a hydrogenation sulfonation reaction catalyst, or (b) an organic peroxide.

The organic hydrogen polyoxyalkylene as a crosslinking agent in the above (a) addition reaction (hydrogenation alkylation reaction) contains at least two hydrogen atoms (SiH groups) bonded to a ruthenium atom in one molecule, and The conventionally known organic hydrogen polyoxyalkylene represented by the following average composition formula (II) can be applied.

R ² _b H _c SiO _(4-bc)/2 (II)

(wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably having no aliphatic unsaturated bond. Specific examples are methyl group, ethyl group, propyl group, butyl group, and pentyl group. An alkyl group such as a hexyl group; an unsubstituted monovalent hydrocarbon group such as a cyclohexyl group, a cyclohexenyl group or a phenyl group; a hydrogen atom of the above monovalent hydrocarbon group such as a 3,3,3-trifluoropropyl group or a cyanomethyl group; a monovalent hydrocarbon group substituted with at least a portion of a substituted alkyl group substituted with a halogen atom or a cyano group, and satisfies: b is 0.7 to 2.1, c is 0.01 to 1.0, and b+c is 0.8 to 3.0, preferably b. 0.8~2.0, c is 0.2~1.0, and b+c is 1.0~2.5)

Further, the molecular structure of the organohydrogenpolysiloxane may be any one of a linear chain, a cyclic chain, a branched shape, and a three-dimensional network. In this case, the number (or degree of polymerization) of the ruthenium atoms in one molecule is from 2 to 300, and particularly preferably from about 4 to 200, which is liquid at room temperature. a hydrogen atom (SiH group) bonded to a halogen atom, which may be located at the end of the molecular chain or the side chain or both. It is used in at least two (usually 2 to 300), preferably three or more (for example, 3 to 200), and preferably about 4 to 150 in one molecule.

Specific examples of the organic hydrogen polyoxyalkylene oxide include 1,1,3,3-tetramethyldioxane, 1,3,5,7-tetramethylcyclotetraoxane, and methyl hydrogen ring. Polyoxyalkylene, methylhydroquinoxane-dimethyloxane cyclic copolymer, tris(dimethylhydroquinoneoxyalkyl)methylnonane, tris(dimethylhydroquinoneoxyalkyl)benzene a ketone, a methyl hydrogen polyoxyalkylene blocked by a trimethylphosphonyl group at both ends, and a dimethyl methoxy alkane-methylhydroioxane copolymer blocked at both ends via a trimethylphosphonium alkyl group a dimethyl phthalocyanine blocked by a dimethyl hydroquinone oxyalkyl group at both ends, and a dimethyl methoxy oxane-methyl hydrazine oxyalkylene copolymer blocked at both ends by a dimethyl hydroquinone oxyalkyl group a methylhydroquinone-diphenyl decane copolymer blocked by a trimethyl decyloxy group at both ends, and a methyl hydro oxane-diphenyl blocked by a trimethyl decyloxy group at both ends Alkoxyoxane-dimethyloxane copolymer, cyclic methyl hydrogen polyoxyalkylene, cyclic methylhydroquinone-dimethyloxane copolymer, cyclic methylhydroquinone - Diphenyl sulfoxane-dimethyl decane copolymer, from (CH ₃ ) ₂ HSiO _1/2 units and SiO ₄ a copolymer composed of _/2 units, a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 unit, SiO _4/2 unit, and (C ₆ H ₅ )SiO _3/2 unit, or the like In the exemplified compound, a part or all of the methyl group is substituted by an alkyl group such as an ethyl group or a propyl group or an aryl group such as a phenyl group.

The amount of the organohydrogenpolyoxane to be added is 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.3 to 10 parts by mass based on 100 parts by mass of the organopolysiloxane of the component (A). Share.

In addition, the organic hydrogen polyoxyalkylene, the bond in the (C) component The molar ratio of the hydrogen atom of the ruthenium atom (i.e., SiH group) to the alkenyl group bonded to the ruthenium atom in the component (A) is 0.5 to 5 moles/mole, preferably 0.8~. 4 Moor / Mo Er, especially good for 1 ~ 3 Mo / Mo Erquan to mix.

Further, the hydrogenation sulfonation reaction catalyst used in the crosslinking reaction of the above (a) addition reaction (hydrogenation alkylation reaction) can be suitably used, and examples thereof include platinum black and platinum (IV) chloride. a reaction product of chloroplatinic (IV) acid, chloroplatinic (IV) acid and a monohydric alcohol, a complex of chloroplatinic (IV) acid and an olefin, a platinum-based catalyst such as platinum acetoacetate, or a palladium system Catalyst, bismuth catalyst, etc. The blending amount of the hydrogenation reaction catalyst can be set to the amount of the catalyst, and is usually converted to a platinum group metal mass, preferably from 1 to 1,000 ppm, more preferably from 5 to 100 ppm. When the amount is less than 1 ppm, the addition reaction is not sufficiently carried out, and there is a concern that the hardening is insufficient, and when it is added in an amount exceeding 1,000 ppm, it is not economical.

Further, in addition to the above reaction catalyst, an addition reaction controlling agent may be used for the purpose of adjusting the curing rate or the use period. Specific examples thereof include ethynylcyclohexanol or tetramethyltetravinylcyclotetraoxane.

On the other hand, (b) organic peroxides include, for example, benzammonium peroxide, 2,4-dichlorobenzidine peroxide, p-methylbenzhydryl peroxide, ortho-methylbenzophenone peroxide. Bismuth, peroxy 2,4-diisopropylbenzene, 2,5-dimethyl-bis(2,5-tri-butylperoxy)hexane, di(tertiary butyl) peroxide, tertiary Butyl perbenzylate, 1,6-hexanediol-bis-tertiary butylperoxycarbonate, and the like.

This (b) organic peroxide is added in an amount relative to the component (A). 100 parts by mass, 0.1 to 15 parts by mass, particularly preferably 0.2 to 10 parts by mass. When the amount of addition is too small, the crosslinking reaction does not proceed sufficiently, and the hardness may be lowered or the strength may be insufficient. When the amount is too large, not only the cost is disadvantageous, but also the decomposition product of the curing agent may be generated in a large amount, and the coloration of the sheet is increased.

In the polyfluorene oxide composition of the present invention, in addition to the above components, a flame retardant imparting agent, a colorant, a carbon functional decane having an alkoxyalkyl group, or the like may be added to the extent that the object of the present invention is not impaired. This is followed by an agent.

The polyfluorene composition of the present invention can be obtained by kneading a predetermined amount of the above components by a twin roll mill, a kneading machine, a Banbury mixer or the like.

The plasticity of the polyfluorene composition thus prepared before curing is 150 to 1,000, preferably 200 to 800, and particularly preferably 250 to 600. When the plasticity is less than 150, it is difficult to maintain the shape of the uncured sheet, and the viscosity is enhanced to make it difficult to use. Further, when it exceeds 1,000, it becomes dry and it is difficult to carry out the flaking step. The plasticity can be measured in accordance with JIS K 6249.

When the polyfluorene-containing composition of the present invention is formed into a sheet shape, the molding method is not particularly limited, and extrusion molding, calender molding, or the like can be used. At this time, the thickness of the polysiloxane composition sheet is preferably 0.05 to 3 mm.

In the unsulfurized polyfluorene composition of the present invention, EVA can be used as a substrate, and EVA can be formed by laminating the surface of one of the polyoxo compositions.

For example, a method of laminating a polyfluorene-containing polyoxonium composition and an EVA is performed by press-forming a sheet in which both layers are laminated by a roll in advance, or by a roll-on-polysiloxane single layer. After press molding, a method of attaching and forming while simultaneously laminating with EVA during the winding process.

The hardening of the polyfluorene composition can be carried out by heating at 120 to 150 ° C for 20 to 60 minutes.

Here, a method of manufacturing a solar cell module according to the present invention is described. The solar cell module has a light-transmissive substrate on a side of a photosensitive surface, and superimposes EVA and a polysulfide composition in an unsulfurized state into a double layer. The structured laminate is placed on the light-transmissive substrate, and the solar cell elements are placed in series on the upper portion of the laminate, and the EVA single layer, or EVA and unfilled, are placed on the back surface of the solar cell element series. The polyfluorene composition in a sulfur state is superposed as a laminate of a two-layer structure, and the inner surface protective material is laminated on the rearmost side, and then heated and pressed under vacuum using a vacuum laminator to form an unsulfurized polyfluorene. The oxygen composition and EVA are crosslinked to form a module.

Example

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. The part of the unit of the blending amount is the mass part. Further, the weight average molecular weight and the weight average polymerization degree are polystyrene-converted values by gel permeation chromatography (GPC) analysis.

[Examples, Comparative Examples]

First, the polyoxane used in the examples and comparative examples will be described.

Addition: consisting of dimethyloxane unit 99.85 mol%, methyl vinyl fluorene oxide unit 0.025 mol%, dimethyl vinyl fluorene oxide unit 0.125 mol%, and the average degree of polymerization is about 100 parts of 6,000 organic polyoxane, 70 parts of cerium oxide (trade name: Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) having a BET specific surface area of 300 m ² /g, and hexamethyldioxane as a dispersing agent The mixture and 4 parts of water were kneaded by a kneading machine, and heat-treated at 170 ° C for 2 hours to prepare a compound.

0.5 parts of C-25A (platinum catalyst)/C-25B (organohydrogen polyoxyalkylene) (all manufactured by Shin-Etsu Chemical Co., Ltd.) as an addition-crosslinking hardener, each of 100 parts of the above compound /2.0 parts, after uniformly mixing by a twin roll machine, a calcined roll of a polysulfide composition was produced by a calender roll.

In addition, the EVA sheet (Fast Cure Type) for solar cells made by Sanvic Co., Ltd. was used as the EVA, and the white plate glass (3.2 mm thick, with the embossed shape on one side) made by Nakajima Glass Industrial Co., Ltd. was used as the light penetration of the surface. For the substrate, a solar cell module of the examples and the comparative examples was produced by using TPT (Tedlar-PET-Tedlar: PTD250) of MA Packaging Co., Ltd. as an inner surface protective material.

That is, the solar cell modules 100 to 600 of the first to sixth embodiments are obtained in accordance with the configurations of the first to sixth embodiments described above.

In addition, the solar cell module 700 shown in FIG. 7 is obtained (Comparative Example) 1). The solar cell module 700 sequentially includes a whiteboard glass as a light-transmitting substrate 101, a sealing material EVA102, a crystallization solar cell element series 104, a sealing material EVA102, and a polyoxyl oxide 103 from the incident direction of sunlight. And the inner surface protective material 105 is composed of.

Fig. 8 is a solar battery module 800 (Comparative Example 2), in order from the incident direction of sunlight, sequentially, a whiteboard glass as a light-transmitting substrate 101, a sealing material EVA102, a matrix of crystalline solar cell elements 104, and a seal. The composite material consists of polyoxyl oxide 103, EVA 102, and inner surface protective material 105.

Fig. 9 is a solar battery module 900 (Comparative Example 3), in order from the incident direction of sunlight, sequentially, a whiteboard glass as a light-transmitting substrate 101, a sealing material EVA 102, a matrix of crystalline solar cell elements 104, and a seal The composite material EVA 102 and the inner surface protective material 105 are formed.

Fig. 10 is a solar cell module 1000 (Comparative Example 4), which is sequentially arranged from the white light glass as the light transmissive substrate 101, the sealing material polyoxyl oxide 103, and the crystallization solar cell element series from the incident direction of sunlight. 104. The sealing material polyoxyl oxide 103 and the inner surface protective material 105 are formed.

Here, the sealing material EVA102 has a thickness of 0.45 mm and is in the form of a sheet. In addition, the sealing material polyxylene oxide 103 has a thickness of 0.5 mm, and the solar cell modules 100 to 700 form a sheet-like shape in which the polyoxygen oxide 103 and the EVA 102 are integrated. That is, the total thickness of the EVA polyoxygenated laminate was 0.95 mm. In the solar cell module 800, the sealing material polyoxane 103 is a monomer having a thickness of 0.5 mm.

In addition, the solar cell module 100 is separately produced without adding The sealing material of the sulfur state has a thickness of 0.05, 0.1, 0.25, 0.5, 1, 3 mm and is integrated with the EVA 102, respectively. Therefore, the thickness of the sealing material EVA polyfluorene oxide laminate is 0.5, 0.55, 0.7, 0.95, 1.45, 3.45 mm, respectively.

Next, each step in the manufacture of each solar cell module will be described.

[Production of solar cell module] [1] Fabrication of EVA polyfluorene laminate sheets

The above polyfluorene oxide composition is formed into a sheet by calendering. In this case, the thickness of the polyfluorene-containing composition of the unsulfurized state was adjusted to be 0.05, 0.1, 0.25, 0.5, 1, and 3 mm thick, and EVA was attached as a base material.

The upper surface of the polysulfide-containing composition of the unsulfurized state is formed by pressing the embossed film while protecting the polyfluorinated surface.

[2] Composition of solar cell components (units)

The solar battery unit 104 is a p-type single crystal unit for a solar cell of 156 mm square.

[3] Production of solar cell components (cells)

The solar cell unit series 104 is arranged in an array of 4 in-line sizes (2 × 2 columns), and is formed by connecting connection wirings in series.

[4] Formation of solar cell modules

The solar battery module 100 is taken as an example for illustration.

In the form that the EVA102 is oriented to contact one side of the whiteboard glass, The EVA polyoxyl composite (102, 103) is placed on top of a whiteboard glass (light-transmitting substrate 101). The solar cell unit series 104 is placed on the polysilicon oxide 103, and the EVA 102 is placed thereon, and the inner surface protective material 105 is finally placed.

The thus obtained glass-sealing material-unit sealing material-inner surface protective material laminate was heated and pressed at 140 ° C under vacuum by a vacuum laminator to form a solar cell module. Between the EVA 102 and the polyoxygen oxide 103, no visually identifiable interface was produced, and wrinkles or undulations were not generated, and the laminate sealing was well performed.

The solar cell module produced by the above steps is such that a frame made of an aluminum alloy is attached to the periphery, and a frame sealing material such as polyfluorinated oxygen is sealed, and finally fixed at a corner portion of the frame by a screw, thereby finally completing the sun. Battery module.

Next, examples and comparative examples of the PID test are shown.

[PID test]

In the solar cell module produced as described above, the photosensitive surface side glass was placed below, and the photosensitive surface side white glass was immersed in the water surface in a water tank, and the test was performed in an environment of a temperature of 60 ° C and a humidity of 85% RH.

A voltage of -1,000 V was applied to the inside of the solar cell between the outer aluminum frame and the solar cell wiring, and was carried out for 96 hours. The output measurement was measured and compared before and after the test by a pulse wave IV simulator. The test conditions were measured at 25 ° C and an illuminance of 1,000 W/m ² .

The results are shown in Tables 1 and 2.

As shown in Table 1, in the solar cell modules 100, 200, 300, 400, 500, and 600, the output maintenance ratio (initial) after the test was 100 ± 0.2%, and it was found that the PID phenomenon was suppressed.

As shown in Table 2, the output maintenance ratios (initial) of the solar cell modules 700 and 800 after the test were 72.6% and 68.9%, respectively, and it was found that the PID phenomenon occurred. This result shows that the PID phenomenon cannot be suppressed when there is no polyoxane between the white-surface glass on the photosensitive surface side and the solar cell unit. Further, in the solar battery module 900, the output maintenance ratio (initial) after the test was 60.1%, and the generation state of the PID phenomenon was the largest.

The solar cell module 1000 has an output maintenance rate of 100.1% after the test, and the PID phenomenon has been suppressed. In this structure, it is considered that the PID resistance of the solar cell module is the largest, but there is a problem in the production cost of the solar cell.

Further, in the solar battery module 100, the evaluation results of changing the thickness of the polyfluorene oxide are shown in Table 3.

As shown in Table 3, the output maintenance ratio was 98.0% at 0.05 mm, and was 100 ± 0.2% when the thickness of the polyfluorene oxide was 0.1, 0.25, 0.5, 1, and 3 mm. When the thickness is 0.05 mm, the PID phenomenon suppressing effect can be obtained, but it is preferably 0.1 mm or more.

As described above, the solar cell module of the present invention uses a composite of EVA and polyfluorene as a sealing material, and laminates the sealing between a penetrating substrate composed of glass or the like and a solar cell unit. By combining the composites, the generation of PID can be suppressed, and a good lamination sealing can be easily obtained without greatly increasing the production cost of the solar cell module.

100‧‧‧Solar battery module

101‧‧‧Light penetrating substrate

102‧‧‧Fitting material EVA

103‧‧‧Flaming material polyoxyl

104‧‧‧Solar battery components

105‧‧‧Inside protective materials

Claims (12)

A solar cell module having a light-transmissive substrate on a photosensitive surface side and a solar cell module having an inner surface protection material on an inner surface side, wherein the photosensitive surface side light-transmitting substrate and the solar cell element are The sealing material between them is a structure in which EVA (ethylene-vinyl acetate copolymer) is laminated adjacent to polyoxymethylene, and the structure between the solar cell element and the inner surface protective material is sealed by EVA. . A solar cell module having a light-transmissive substrate on a photosensitive surface side and a solar cell module having an inner surface protection material on an inner surface side, wherein the photosensitive surface side light-transmitting substrate and the solar cell element are The sealing material is a structure in which EVA (ethylene-vinyl acetate copolymer) is laminated adjacent to polyoxymethylene, and is between the inner surface protective material and the solar cell element, EVA (ethylene-acetic acid) A structure in which a vinyl ester copolymer is laminated adjacent to a polyfluorene oxide. The solar cell module of claim 1, wherein the EVA is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent polyoxygen is in contact with the solar cell element. The solar cell module of claim 1, wherein the polyoxygen is in contact with the photosensitive surface side light transmissive substrate, and the adjacent EVA is in contact with the solar cell element. The solar cell module of claim 2, wherein the EVA is respectively in contact with the light-transmissive substrate on the photosensitive surface side and the inner surface protection material, and adjacent to each other The helium oxygen is in contact with the structure of the solar cell element, respectively. The solar cell module of claim 2, wherein the polyoxynium is in contact with the light-transmitting substrate on the photosensitive surface side and the inner surface protective material, and the adjacent EVAs are respectively in contact with the structure of the solar cell element. The solar cell module of claim 2, wherein the EVA is in contact with the light-transmissive substrate on the photosensitive surface side, and the adjacent polyfluorene is in contact with the photosensitive surface of the solar cell element, and the polysilicon is in contact with the inner surface protection. The material, the adjacent EVA is in contact with the inner surface of the solar cell element. The solar cell module of claim 2, wherein the polyoxygen is in contact with the light-transmitting substrate on the photosensitive surface side, and the adjacent EVA is in contact with the photosensitive surface of the solar cell element, and the EVA is in contact with the inner surface protective material, The polybutoxide adjacent thereto is in contact with the inner surface of the solar cell element. The solar cell module according to any one of claims 1 to 8, wherein the EVA and the polyfluorene oxygen form a composite laminate in which the EVA and the polyfluorene are superposed into a two-layer structure, and the thickness of the polyoxygenated oxygen is 0.05 to 3 mm. The thickness of the composite laminate is 0.45 to 3.6 mm. The solar cell module according to any one of claims 1 to 8, wherein the polyfluorene oxide is a cured product comprising the following poly (A) to (C) polyoxo-oxygen composition, (A) having the following average composition formula; (I) is an organopolyoxyalkylene having a degree of polymerization of 100 or more, 100 parts by mass of R ¹ _a SiO _(4-a)/2 (I) (wherein R ¹ is an unsubstituted or substituted group of the same or different species) The monovalent hydrocarbon group, a is a positive number of 1.95 to 2.05) (B) 20 to 150 parts by mass of the reinforcing cerium oxide having a specific surface area of 50 m ² /g or more (C) an effective amount of the hardening agent to harden the component (A). The solar cell module according to any one of claims 1 to 8, wherein the inner surface light transmissive substrate is used as the inner surface protective material. A method for manufacturing a solar cell module according to any one of claims 1 to 8, characterized in that the solar cell module has a light-transmissive substrate on the photosensitive surface side, and the EVA and the unsulfurized state are The laminate of the polyfluorene composition having a two-layer structure is placed on the light-transmissive substrate, and the solar cell elements are placed in series on the upper portion of the laminate, and are placed on the back surface of the solar cell element series. EVA single layer, or a combination of EVA and unsulfurized polyfluorene oxide composition as a two-layer structure, after the inner surface protective material is laminated on the most back side, and then heated under vacuum using a vacuum laminator Pressing, the polysulfide composition of the unsulfurized state and the EVA are crosslinked to be modularized.