KR20180132709A - An ion trapping agent for a solar cell, a composition for encapsulating the solar cell comprising the ion trapping agent, - Google Patents

Abstract

The ion trapping agent for solar cells of the present invention is characterized in that (A) at least a part of the ion exchanger is substituted with at least one ion (a1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion -Zincium phosphate, and (B) at least one of the? -Tri phosphate in which at least a part of the ion exchanger is substituted with at least one ion (b1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion Contains one side.

Description

An ion trapping agent for a solar cell, a composition for encapsulating the solar cell comprising the ion trapping agent,

The present invention relates to an ion trapping agent for a solar cell which selectively adsorbs Na ⁺ ions which cause PID (Potential Induced Degradation) of a solar cell and gives a solar cell excellent in PID resistance, and a solar cell sealing agent Compositions and solar cell modules.

Solar cells as a clean energy source are being used because of rising awareness of environmental problems. Generally, a solar cell is a composite comprising a plurality of solar cell modules. The solar cell module includes a front side transparent protective member, a layer sealed with the solar cell element, and a back side protective member (back sheet) .

In recent years, large-scale photovoltaic power generation systems called megasolor have been rapidly increasing, in which a large number of crystal silicon solar cell modules are installed on a large site and a photovoltaic power generation system for power business is built. In such a large-scale solar power generation system, in order to simplify the wiring work of the solar cell modules and to reduce the cost by reducing the number of wiring and the number of connection boxes, a plurality of solar cell modules are connected in series and the maximum system voltage is set to about 600V to 1000V It is often the case that it is designed to be high. However, in such a crystalline silicon solar power generation system having such a high system voltage, there is a case where a rapid characteristic deterioration phenomenon called PID occurs in the crystalline silicon solar cell module.

The PID phenomenon of such a crystalline silicon solar cell module has not yet been fully explained in terms of cause and mechanism. However, it has been reported that the PID phenomenon is likely to occur and proceed when a high system voltage is applied to the solar cell module and a high temperature or high humidity state is reached, and the characteristics are restored by applying a high voltage in the reverse direction to the solar cell module have.

Hereinafter, a mechanism in which a PID phenomenon occurs in a crystalline silicon solar cell module using a crystalline silicon solar cell constructed using a general P type wafer will be described. The surface of the crystalline silicon solar cell module is typically covered with a cover glass containing soda lime glass. Here, if moisture is present on the surface of the cover glass, sodium ions (Na ⁺ ions), which are metal ions, are generated from the soda lime glass. The cover glass of the crystalline silicon solar cell module is supported by a metal frame, and the metal frame is connected to the ground and becomes a ground potential.

In this state, when a negative system voltage is applied to the internal wiring of the crystalline silicon solar cell module, a large potential difference occurs inside and outside the crystalline silicon solar cell module. The Na ⁺ ions (metal ions) on the surface of the cover glass move in the cover glass or in the sealing resin due to this potential difference to reach the surface of the crystalline silicon solar cell. Under the conditions of high temperature and high humidity, the volume resistance of the cover glass or the sealing resin is lowered, the leakage current is increased, and Na ⁺ ions (metal ions) are liable to move.

Normally, the surface of the doped layer (N-type) on the light incident side of the crystalline silicon solar cell is covered with an insulating passivation film. This passivation film is polarized by the adhering of the charged ions. As a result, a polarity reverse region (P type) is formed in the vicinity of the interface with the passivation layer of the doped layer (N type) on the light incidence side of the crystalline silicon solar cell and the movement of the light generating carrier can be prevented, The characteristics are degraded.

As a method for preventing the occurrence of the PID phenomenon, several methods have been proposed so far. For example, as a method for coping with a solar power generation system, there is known a method of using an inverter with an insulation transformer and grounding the negative electrode of the inverter input so that the inside of the solar cell module does not become a negative potential with respect to the outside. However, in recent years, transisation has been proceeding in order to achieve high efficiency of the inverter and cost reduction, and it is difficult to cope with such a system.

On the other hand, as a countermeasure for a solar cell module, Patent Document 1 discloses a solar cell module in which a solar cell is sealed using an EVA, in order to prevent penetration of water vapor into the inside of the solar cell module, And an ionomer resin layer is provided on the side opposite to the solar cell.

In addition, although the improvement of the PID phenomenon is not directly aimed at, it has been studied to increase the volume resistivity of the sealing material. Patent Document 2 discloses a solar cell sealing material in which a silane coupling agent having 4 or less carbon atoms of a functional group directly bonding to a silicon atom is added in a proportion of 5 parts by weight or less based on 100 parts by weight of an ethylene / vinyl acetate copolymer . Patent Document 3 discloses that when the total amount of a structural unit derived from ethylene and a structural unit derived from an unsaturated ester and having a total of a structural unit derived from ethylene and a structural unit derived from an unsaturated ester is 100 mass% Discloses a solar cell sealing material obtained by using a resin composition containing 0.001 to 5 parts by mass of meta kaolin per 100 parts by mass of an ethylene-unsaturated ester copolymer having an ester-derived structural unit in an amount of 20 to 35% by mass .

Patent Document 4 discloses a resin composition for a solar cell encapsulant containing an ethylene copolymer and an inorganic ion trapping agent selected from the group consisting of an oxide of a pentavalent metal, an oxide of a hexavalent metal, an oxide of a hexavalent metal, .

Japanese Patent Application Laid-Open No. 2011-77172 Japanese Patent Application Laid-Open No. 11-54766 Japanese Patent Application Laid-Open No. 2013-64115 Japanese Patent Application Laid-Open No. 2015-138805

Patent Document 4 describes an example of using zirconium phosphate (inorganic ion exchanger) as a metal phosphate salt. However, the ion trapping agent captures Na ⁺ ions but does not sufficiently and also releases H ⁺ ions by ion exchange Therefore, depending on the constitution, there is a problem that the pH is lowered, adversely affecting the sealing resin, or corrosion of constituent members of the solar cell element such as electrodes is promoted.

An object of the present invention is to provide an ion trapping agent for a solar cell which selectively adsorbs Na ⁺ ions which cause PID of a solar cell.

Another object of the present invention is to provide a solar cell encapsulant composition which suppresses corrosion of constituent members of a solar cell element such as electrodes and the like, which are caused by PID, and a long-life solar cell module.

The present inventors have found that an α-zirconium phosphate in which at least a part of an ion exchanger is substituted with at least one ion selected from lithium ion, potassium ion, rubidium ion, cesium ion, magnesium ion and calcium ion, ion, potassium ion, cesium ion, rubidium ion, magnesium ion, and at least one ion substituted solar cell ion scavenger containing at least one of the α- titanium phosphate compound selected from calcium ion I, the Na ⁺ ions caused by PID And the present inventors have completed the present invention.

1. An α-zirconium phosphate wherein at least a part of the ion exchanger (A) is substituted with at least one ion (a1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion, Characterized in that at least a part of the ion exchanger contains at least one of? -Titrate substituted with at least one ion (b1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion Ion trap agent for solar cell.

2. The ion trapping agent for a solar cell according to 1 above, wherein the component (A) is? -Phosphoric acid in which 0.1 to 6.7 meq / g of the total ion exchange capacity is substituted with the ion (a1).

3. The ion trapping agent for a solar cell according to 1 or 2 above, wherein the? -Phosphorus zirconium salt before being substituted with the ion (a1) is a compound represented by the following formula (1).

_{Zr 1-x Hf x H a} (PO 4) b · mH 2 O (1)

(Wherein, 0? X? 0.2, 2 <b? 2.1, a is a positive number satisfying 3b-a = 4 and 0? M? 2)

4. The ion trapping agent for solar cells according to any one of 1 to 3 above, wherein the component (B) is? -Phosphate in which 0.1 to 7.0 meq / g of the total ion exchange capacity is replaced with the ion (b1) .

5. The ion trapping agent for a solar cell according to any one of items 1 to 4, wherein the? -Phosphate before substitution with the ion (b1) is a compound represented by the following formula (2).

_{TiH s (PO 4) t ·} nH 2 O (2)

(Where 2 < t &lt; = 2.1 and s is a positive number satisfying 3t-s = 4 and 0? N? 2)

6. An encapsulating composition for a solar cell, comprising the ion trapping agent for a solar cell according to any one of 1 to 5 and a resin.

7. The encapsulant composition for a solar cell according to 6 above, wherein the resin comprises an ethylene-vinyl acetate copolymer resin.

8. The solar cell element according to any one of claims 1 to 7, wherein between the front-side transparent protective member, the back-side protective member, the solar cell element, and the front-side transparent protective member and the back- Wherein the solar cell module comprises a sealing layer that is sealed using a composition.

The ion trapping agent for a solar cell of the present invention highly adsorbs Na ⁺ ions that cause PID of a solar cell and is difficult to release H ⁺ ions. Therefore, a decrease in the output caused by the PID is suppressed. Further, the encapsulant composition for a solar cell of the present invention can inhibit the corrosion of the constituent members of the solar cell element such as an electrode, and can provide a long-life solar cell module.

1 is a schematic cross-sectional view showing a solar cell module of the present invention.

Hereinafter, the present invention will be described in detail.

1. Ion pickers for solar cells

The ion trapping agent for solar cells of the present invention is characterized in that (A) at least a part of the ion exchanger is substituted with at least one ion (a1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion (Hereinafter referred to as &quot; ion trapping agent (A) for a solar cell &quot;), and (B) at least a part of the ion exchanger is at least one selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion (Hereinafter referred to as &quot; ion trapping agent (B) for a solar cell &quot;) substituted with one kind of ion (b1). Ion exchangers are typically proton.

In the present invention, the ion trapping material for a solar cell can be formed by, for example, a solar cell element 11 constituting the solar cell module 10 shown in FIG. 1, a sealing layer 12 sealing the solar cell element 11 with resin, Is contained in at least one of the sealing layer (13) including the resin, the front side transparent protective member (15), and the back side protective member (17) We can plan renown. That is, since the ion trapping agent for a solar cell of the present invention does not emit proton (H ⁺ ), the constituent members of the solar cell are prevented from being decomposed or altered, and output reduction is suppressed.

Since zirconium phosphate before being substituted with the ion (a1) and? -Phosphate before being substituted with the ion (b1) all contain OH groups in the layer, lithium ions, potassium ions, rubidium ions, It is considered that Na ⁺ ions are selectively adsorbed without releasing H ⁺ ions by adopting a structure in which a cesium ion, a magnesium ion, or a calcium ion is substituted.

Since the ion trapping agent for solar cells of the present invention is neutral, even when added to an electrolytic solution, its pH is not significantly changed. When the sealing layer 13 contains an alkaline or acidic substance, the resin may be decomposed with a change in pH. For example, when the resin includes an ethylene-vinyl acetate copolymer resin, acetic acid or the like is easily generated and is connected to deterioration of the solar cell. However, if the sealing layer includes the ion trapping agent for a solar cell of the present invention, There is nothing to happen.

Further, since the ion trapping agent for a solar cell of the present invention is an inorganic compound, it is excellent in thermal stability and stability in a solvent. Therefore, when contained in the constituent member of the solar cell, it is stable even in the state where the charge is applied.

1-1. Ion capturing agent for solar cell (A)

The ion trapping agent (A) for a solar cell of the present invention is a substitution product of zirconium a-phosphate (a1) as described above.

The? -Phosphoric zirconium is a compound represented by the following formula (1).

_{Zr 1-x Hf x H a} (PO 4) b · mH 2 O (1)

(Wherein 0? X? 0.2, 2 < b? 2.1 and a is a number satisfying 3b-a = 4 and 0? M? 2)

Since the ion exchanger of zirconium phosphate is usually a proton, part or all of the proton is replaced with an ion (a1) to form the ion trapping agent (A) for a solar cell of the present invention. The ion (a1) is at least one selected from the group consisting of lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion, and from the viewpoint of good trapping property of Na ⁺ ion, an ion derived from a monovalent alkali metal element Lithium ion, potassium ion, rubidium ion or cesium ion).

In the ion trapping agent (A) for a solar cell of the present invention, the amount of the substituted ion (a1) is preferably 0.1 to 6.7 meq / g, more preferably 1.0 to 6.7 meq / g. Further, from the viewpoint of Na ⁺ ion-adsorbing ability, it is more preferably 3.5 to 6.7 meq / g.

X in the formula (1) is preferably 0? X? 0.1, more preferably 0? X? 0.02, from the viewpoint of the ability to capture Na ⁺ ions. When Hf is included, it is preferably 0.005? X? 0.1, more preferably 0.005? X? 0.02. When x> 0.2, the ion exchange performance by the ion (a1) is improved, but since radioactive isotopes are present, adverse effects may occur when the constituent parts of the solar cell include electronic parts.

The method for producing the ion trapping agent (A) for a solar cell of the present invention is not particularly limited. For example, in the case of preparing zirconium phosphate substituted with lithium ion, zirconium phosphate may be added to an aqueous solution of lithium hydroxide (LiOH), stirred for a predetermined period of time, filtered, washed and dried . The concentration of the LiOH aqueous solution is not particularly limited. In the case of a high concentration, the basicity of the reaction solution is high and a part of the? -Phosphoric acid zirconium may be eluted. Therefore, it is preferably 1 mol / L or less, more preferably 0.1 mol / L or less.

In the case of producing? -Phosphoric zirconium substituted with potassium ion, the same ion exchange method as described above can be applied.

In the case of producing zirconium aphosphate substituted with a magnesium ion or a calcium ion, since the hydroxide of magnesium or calcium is difficult to dissolve in water, it is first replaced with an alkali metal ion such as potassium and then an aqueous solution of magnesium chloride or the like is used . In addition, for example, zirconium phosphate may be added to an aqueous solution of magnesium acetate and the same operation may be carried out.

1-2. Ion capturing agent for solar cell (B)

As described above, the ion trapping agent (B) for a solar cell of the present invention is a substituent by the ion (b1) of? -Phosphate.

The above-mentioned? -Phosphate is a compound represented by the following formula (2).

_{TiH s (PO 4) t ·} nH 2 O (2)

(Where 2 < t &lt; = 2.1 and s is a number satisfying 3t-s = 4 and 0 &

Since the ion exchanger of? -phosphate is usually a proton, part or all of the proton is substituted by the ion (b1) to form the ion trapping agent (B) for the solar cell of the present invention. The ion (b1) is at least one selected from the group consisting of lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion, and from the viewpoint of good trapping property of Na ⁺ ion, an ion derived from a monovalent alkali metal element Lithium ion, potassium ion, rubidium ion or cesium ion).

In the ion trapping agent (B) for a solar cell of the present invention, the amount of the substituted ion (b1) is preferably 0.1 to 7.0 meq / g, more preferably 1.0 to 7.0 meq / g. Further, from the viewpoint of Na ⁺ ion-adsorbing ability, it is more preferably 3.5 to 7.0 meq / g.

The method for producing the ion trapping agent (B) for a solar cell of the present invention is not particularly limited and may be the same as the method for producing the ion trapping agent (A) for a solar cell.

The ion trapping agent for a solar cell of the present invention usually has a layered structure, and the upper limit of the median particle size is preferably 5.0 占 퐉, more preferably 3.0 占 퐉, and further preferably 2.0 占 퐉, , Preferably 0.5 mu m. The preferred particle size may be selected depending on the type of the constituent member to which the ion trapping agent for a solar cell of the present invention is applied.

The moisture content of the ion trapping agent for a solar cell of the present invention is preferably 10 mass% or less, more preferably 5 mass% or less. When the content of moisture is 10 mass% or less, occurrence of gas caused by electrolysis of water in the case of forming a member constituting a solar cell can be suppressed, and the problem of the battery can be suppressed. The water content can be measured by the Karl Fischer method.

When the water content of the ion trapping agent for a solar cell is 10 mass% or less, there is no particular limitation, and a commonly used powder drying method can be applied. For example, there is a method of heating at 100 to 300 캜 for 6 to 24 hours under atmospheric pressure or reduced pressure.

2. Sealant composition for solar cell

The encapsulant composition for a solar cell of the present invention is characterized by containing the above-described ion trapping agent for a solar cell of the present invention and a resin. The encapsulant composition for a solar cell of the present invention may contain other components such as a crosslinking agent, a crosslinking aid, an adhesion improver, an ultraviolet absorber, a light stabilizer, and an antioxidant described below.

The encapsulant composition for a solar cell of the present invention can be applied to a sealing layer 13 between a front side transparent protective member 15 and a back side protective member 17 constituting the solar cell module 10 shown in Fig. Lt; / RTI &gt;

As the resin contained in the encapsulant composition for a solar cell of the present invention, ethylene-vinyl acetate copolymer resin; Polyolefin resins such as polyethylene and polypropylene; Ionomer resins; Ethylene / methacrylic acid copolymer; Ethylene / methacrylic acid ester copolymer; Ethylene-acrylic acid copolymer; Ethylene-acrylic acid ester copolymers; Polyvinyl fluoride resin; Polyvinyl chloride resin, and the like. Of these, an ethylene-vinyl acetate copolymer resin is particularly preferable in that a sealing layer having excellent transparency can be formed.

The ethylene-vinyl acetate copolymer resin is not particularly limited, but when the solar cell module is manufactured, for example, after the vacuum heat lamination process, the heat resistance at 100 ° C to 150 ° C is smoothly It is preferable to use an ethylene-vinyl acetate copolymer resin in which the content of the structural unit derived from vinyl acetate is preferably 20 to 40 mass%, more preferably 25 to 35 mass%, and still more preferably 28 to 33 mass% desirable.

The melt mass flow rate (MFR) of the ethylene-vinyl acetate copolymer resin is preferably 1 g to 40 g / 10 min, more preferably 15 g to 40 g / 10 min in accordance with the method (190 ° C) according to JIS K 7210 . The Vicat softening point is preferably 30 占 폚 to 40 占 폚 in the method according to JIS K 7206.

In the encapsulant composition for a solar cell according to the present invention, the content ratio of the ion trapping agent for a solar cell is preferably 100% by mass or less in view of the transparency of the encapsulating layer and the ability to capture Na ⁺ ions in the encapsulating layer , Preferably 0.01 to 1.0 part by mass, and more preferably 0.05 to 0.5 part by mass. The median particle diameter of the ion trapping agent for a solar cell is preferably 0.5 to 5.0 占 퐉, more preferably 0.7 to 2.0 占 퐉, from the viewpoint of power generation efficiency of the solar cell.

The encapsulant composition for a solar cell of the present invention may contain other components as described above.

As the crosslinking agent, organic peroxides, azo compounds, tin compounds and the like can be used. These may be used alone or in combination of two or more.

Examples of the organic peroxide include hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane; Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl- Dialkyl peroxides such as di (tert-peroxy) hexyne-3; Diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy pivalate, tert-butyl peroxy octoate, tert-butyl peroxyisopropyl carbonate, Peroxybenzoate, di-tert-butyl peroxyphthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5- 3, and tert-butylperoxy-2-ethylhexylcarbonate; And ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide.

Examples of the azo compound include azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile).

Examples of the tin compound include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, and dioctyltin dilaurate.

When the composition for a solar cell according to the present invention contains a crosslinking agent, the content thereof is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 1.5 parts by mass, more preferably 0.05 to 1.5 parts by mass when the content of the resin is 100 parts by mass to be.

The crosslinking aid accelerates a crosslinking reaction by a crosslinking agent, and is preferably a polyfunctional monomer having at least one of a carbon atom-carbon atom double bond and an epoxy group, more preferably an allyl group, a methacryloyl group, Vinyl groups, and the like. Specific examples thereof include polyallyl compounds, poly (meth) acryloxy compounds, epoxy compounds, and the like. These may be used alone or in combination of two or more.

Examples of the polyallyl compound include triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, and diallyl maleate.

Examples of the poly (meth) acryloxy compound include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6- Hexanediol diacrylate, and 1,9-nonanediol acrylate.

Examples of the epoxy compound include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, Cydyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, and the like.

When the sealing composition for a solar cell of the present invention contains a crosslinking aid, the content thereof is preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 2.0 parts by mass when the content of the resin is 100 parts by mass Wealth.

The adhesiveness improver is preferably a silane compound having a polymerizable unsaturated bond-containing group such as a methacryloyl group, an acryloyl group, or a vinyl group, or a hydrolyzable group such as an alkoxy group, and a conventionally known silane coupling agent may be used .

Examples of the silane coupling agent include vinyl trichlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? - (3 (Aminoethyl) gamma -aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma -amino &lt; RTI ID = 0.0 & Aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, have.

When the composition for a solar cell according to the present invention contains an adhesion improver, the content thereof is preferably 0.01 to 3.0 parts by mass when the content of the resin is 100 parts by mass.

Examples of the ultraviolet absorber include benzophenone-based compounds, benzotriazole-based compounds, triazine-based compounds, and salicylic acid ester-based compounds. These may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2- 4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- Methyl-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di- tert-butylphenyl) benzotriazole, 2- -3,5-dimethylphenyl) -5-methoxybenzotriazole , 2- (2-hydroxy-5-tert-butylphenyl) -5-chlorobenzotriazole, 2- 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) , 3,5-triazin-2-yl) -5- (hexyloxy) phenol, phenyl salicylate, and p-octylphenyl salicylate.

When the composition for a solar cell according to the present invention contains an ultraviolet absorber, the content thereof is preferably 0.01 to 3.0 parts by mass when the content of the resin is 100 parts by mass.

The light stabilizer is not particularly limited as long as it can capture radicals generated by photo deterioration, and hindered amine compounds, thiol compounds, thioether compounds and the like can be used. These may be used alone or in combination of two or more.

As the light stabilizer, hindered amine compounds are preferable, and specific examples thereof include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine pearlescent Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl- 4-piperidyl) imino} hexamethylene {{2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine- Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-tert-4-hydroxybenzyl) , 2,2,6,6-pentamethyl-4-piperidyl), and the like.

When the solar cell encapsulant composition of the present invention contains a light stabilizer, the content thereof is preferably 0.01 to 3.0 parts by mass when the content of the resin is 100 parts by mass.

The antioxidant is not particularly limited as long as it imparts heat stability to the thermal energy of sunlight, and a monophenol compound, a bisphenol compound, a polymer phenolic compound, a sulfur compound, a phosphoric acid compound, or the like can be used. These may be used alone or in combination of two or more.

Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl- butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [{1,1- 5-undecane, 1,1,3-tris- (2-methylphenyl) propionyloxy} ethyl} Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- (3,3'-bis-4'-hydroxy-propane-1-carboxylic acid methyl ester) 3'-tert-butylphenyl) butyric acid} glucoester, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiopropionate , Triphenylphosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis- (3-methyl-6-tert- butylphenyl-di- tridecyl) phosphite , Cyclic neopentanetetraylbis (octadecylphosphite), trisdiphenylphosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxides such as 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis 2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-tert-butylphenyl) octylphosphite and the like.

When the sealing composition for a solar cell of the present invention contains an antioxidant, the content thereof is preferably 0.05 to 3.0 parts by mass when the content of the resin is 100 parts by mass.

The encapsulant composition for a solar cell of the present invention can be prepared by mixing raw material components, but it is preferable that the ion trapping agent for solar cells, other components, etc. are dispersed in the parent phase with the resin as a parent phase. Particularly, when a component such as a cross-linking agent and a component forming a cross-linking structure is blended, it is preferable that the resin is contained in an uncrosslinked or semi-crosslinked state.

Therefore, in the case of forming the sealing layer 13 in Fig. 1, for example, the sealing composition for a solar cell of the present invention is kneaded and then introduced into an extruder and molded into a thin film by T-die molding or calender molding It is preferable to use a sealing material sheet for an uncrosslinked or semi-crosslinked solar cell module which is obtained by processing into a predetermined size.

3. Solar module

1, the solar cell module of the present invention includes a solar cell element 11, a front side transparent protective member 15, a back side protective member 17, A solar cell element 11 is provided between the member 15 and the back side protective member 17 with a sealing layer 13 which is sealed by using the sealing composition for a solar cell of the present invention. The solar cell elements 11 are connected to each other by the inter connecter 19. In Fig. 1, the current collecting electrodes and the like are omitted.

The solar cell element 11 has a function of converting light incident on a light receiving surface by electricity to a electricity, and preferably includes silicon, a compound semiconductor, and the like.

The sealing layer 13 is preferably a layer containing a crosslinking resin composition formed by using a sealing composition for a solar cell containing a crosslinking agent and the solar cell element 11 and the interconnector 19 are disposed at a predetermined position As shown in Fig.

The front surface side transparent protective member 15 generally includes a material excellent in weather resistance, resistance to wind pressure, abrasion resistance, etc., and may include a resin such as a polyester resin, a polycarbonate resin, or glass. Usually, glass such as soda lime glass is included.

The back side protective member 17 usually includes a material having excellent weather resistance such as a moisture-decomposable polyethylene terephthalate resin and a polyvinyl fluoride resin. The back side protective member 17 may have the function of reflecting the light transmitted through the sealing layer 13.

The method for manufacturing the solar cell module of the present invention is not particularly limited, and conventionally known methods can be applied. For example, a sealing material sheet for an uncrosslinked or semi-crosslinked solar cell module obtained by using a back side protective member and a sealing composition for a solar cell containing a crosslinking agent, a solar cell element, and a sealing material for a solar cell containing a crosslinking agent A sealing material sheet for an uncrosslinked or semi-crosslinked solar cell module obtained by using a composition, and a surface-side transparent protective member are laminated in this order to obtain a laminate, and then the laminate is subjected to vacuum heat lamination And the like. The solar cell element is embedded between the sealing material sheets for the two solar cell modules by the vacuum heat lamination to form a crosslinked resin composition and the sealing layer and the back side protective member containing the same and the front side transparent protective member And the sealing layer are adhered and integrated with each other to manufacture the solar cell module of the present invention.

In the solar cell module of the present invention, since the sealing layer 13 contains a special ion capturing agent, it is possible not only to capture water penetrated into the sealing layer 13 during use of the solar cell and acid generated in hydrolysis Induced degradation (PID) of the solar cell element 11 from the glass to the sealing layer 13 in the case where the front surface side transparent protective member includes glass, Even when sodium ions (Na ⁺ ions), which are the main cause of the decrease in the output power due to the high voltage applied to the solar cell module 10, can be prevented from diffusing, the output reduction of the solar cell module 10 can be suppressed.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

1. Evaluation Method

(1) pH measurement

The pH of the aqueous solution after the addition of the ion trapping agent in the following (2) or the water extracted in the following (3) was measured with a glass electrode type hydrogen ion concentration indicator "D-51" (type name) manufactured by Horiba Seisakusho Co., Respectively. The measurement is in accordance with JIS Z 8802 &quot; pH measurement method &quot;, and the measurement temperature is 25 ° C.

(2) Na ⁺ ion adsorption capacity of ion trapping agent for solar cell in NaCl aqueous solution

Na ⁺ ion adsorption capacity of ion trapping agent for solar cell was evaluated by ICP emission spectrometry. The specific evaluation method is as follows.

First, 0.254 g of NaCl was dissolved in 1 L of water to prepare an aqueous solution having 100 ppm of Na ⁺ ions. The ionic capturing agent was added to the aqueous solution so as to have a concentration of 1.0% by mass, sufficiently mixed, and allowed to stand. Then, after the ion trapping agent was added, the Na ⁺ ion concentration after 8 hours was measured by means of an ICP emission spectrometer "iCAP7600 DUO" (type name) manufactured by Thermo Fisher Scientific Inc. Then, the Na ⁺ ion capture ratio was determined by the following formula.

Na + ion capture ratio = ((initial concentration (100 ppm) - Na ⁺ ion concentration after test (after 8 hours)) / initial concentration (100 ppm)) × 100

(3) Na ⁺ ion adsorption capacity of the crosslinked resin test piece formed using the solar cell encapsulant composition

, 1.0 part by mass of an ion trapping agent for a solar cell, 100 parts by mass of an ethylene-vinyl acetate copolymer resin &quot; EV150R &quot; (trade name) manufactured by Mitsui DuPont Polychemical Co., Ltd. and 10 parts by mass of tert- butylperoxy-2-ethylhexyl carbonate 0.5 part by mass of "Luperox TBEC" (trade name, a crosslinking agent) and 0.5 part by mass of "Luperox 101" (trade name, cross-linking agent) of 2,5-dimethyl-2,5-di (tert- butylperoxy) , 1.0 part by mass of trimethylolpropane trimethacrylate "SR350" (trade name, a crosslinking aid) manufactured by Sartomer, 1.0 part by mass of triallyl isocyanurate "SR533" (trade name, a crosslinking aid) manufactured by Sartomer, And 0.025 parts by mass of sodium chloride of Shidagaku KK were mixed to obtain a composition for a solar cell encapsulant. An injection molding machine "M-50A (II) -DM" (model name) manufactured by Meiki Seisakusho Co., Ltd. was used, Thus, a crosslinked resin test piece (110 mm x 110 mm x 2 mm). The sodium chloride is such that the amount of sodium to the ethylene-vinyl acetate copolymer resin is about 100 ppm in order to remarkably different the measured value of Na ⁺ ion concentration between the examples and the comparative examples.

Subsequently, 10 g of the crosslinked resin test piece was cut into a small piece (about 5 mm x 5 mm x 2 mm) and placed in a 100 mL plastic container together with 50 mL of pure water, and the stopper was closed. Then, this poly container was allowed to stand at 95 DEG C for 20 hours. From the crosslinked resin test pieces, analysis of extracted water containing components eluted into pure water and pH measurement were carried out. Na ⁺ ion concentration was measured by ICP emission spectroscopy. Further, acetic acid concentration was measured by ion chromatography.

2. Preparation and evaluation of ion trapping agent

Example 1

0.272 mol of zirconium oxychloride octahydrate was dissolved in 850 mL of pure water, and 0.788 mol of oxalic acid dihydrate was added to dissolve it. While stirring the aqueous solution, 0.57 mol of phosphoric acid was added. This was refluxed at 103 DEG C for 8 hours while stirring. After cooling, the resulting precipitate was thoroughly washed with water and then dried at 150 DEG C to obtain scaly flour containing zirconium phosphate. The zirconium phosphate was analyzed and found to be zirconium phosphate (H type) (hereinafter referred to as "? -Phosphoric zirconium (Z1)").

Zirconium phosphate (Z1) was self-dissolving in nitric acid with addition of hydrofluoric acid, and then subjected to ICP emission spectrometry analysis to obtain the following composition formula.

ZrH _2.03 (PO ₄ ) _2.01 · 0.05H ₂ O

The median diameter of the zirconium phosphate (Z1) was measured by a laser diffraction particle size distribution analyzer "LA-700" (model name) manufactured by Horiba Seisakusho Co., and found to be 0.9 탆.

Subsequently, 25 g of zirconium phosphate (Z1) was added with stirring to 1000 mL of 0.1N-LiOH aqueous solution, which was stirred for 8 hours. Thereafter, the precipitate was washed with water and vacuum-dried at 150 캜 for 20 hours to prepare lithium ion-substituted? -Phosphoric zirconium containing Zr Li _1.03 H _1.00 (PO ₄ ) _2.01? 0.05H ₂ O. The water content by the Karl Fischer method was 0.5%. In this lithium ion-substituted zirconium phosphate, 4 meq / g of all the cation exchange capacity is substituted with lithium ion. Quot; 4meq-Li substituted zirconium ai phosphate A1-1 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-Li substituted zirconium a-phosphate A1-1. The results are shown in Table 1.

Example 2

0.1N-LiOH, except that the amount of the aqueous solution to 2500mL, Example 1, the operation was performed to, any cation-exchange (cation exchange capacity: 6.7meq / g) is substituted by lithium ion, _2.03 ZrLi (PO _{4) 2.01} - Lithium ion substituted type? -Phosphoric zirconium containing 0.05H ₂ O was produced. The moisture content was 0.3%. Hereinafter, &quot; the entire Li-substituted zirconium alpha -phosphate A1-2 &quot;

Subsequently, various evaluations were carried out using the ion trapping material for a solar cell containing the entire Li-substituted zirconium? -Phosphate A1-2. The results are shown in Table 1.

Example 3

Instead of 0.1N-LiOH aqueous solution, 0.1N-KOH aqueous solution was used, is performed in the same manner as in Example _{1, ZrK 1.03 H 1.00 (PO} 4) 2.01 · 0.03H ₂ O containing type potassium substituted α- phosphate Zirconium. The water content was 0.5%. In this potassium-substituted? -Phosphate zirconium, 4 meq / g of all the cation exchange capacity are substituted with lithium ions. Quot; 4meq-K substituted zirconium a-phosphate A1-3 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-K-substituted zirconium a-phosphate A1-3. The results are shown in Table 1.

Example 4

0.1N-KOH, except that the amount of the aqueous solution to 2500mL, carried out in the same manner as in Example 3, all of cation exchange groups: the (cation exchange capacity of 6.7meq / g) is replaced with potassium ions, ZrK _2.03 (PO _{4) 2.01} To prepare potassium-substituted? -Phosphate zirconium. The water content was 0.4%. Hereinafter, &quot; all-K-substituted zirconium alpha-phosphate A1-4 &quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire K-substitution zirconium a-phosphate A1-4, and the results are shown in Table 1.

Example 5

After 0.272 mol of zirconium oxychloride octahydrate having a Hf content of 0.18% was dissolved in 850 mL of deionized water, 0.788 mol of oxalic acid dihydrate was added and dissolved. While stirring the aqueous solution, 0.57 mol of phosphoric acid was added. This was refluxed at 98 占 폚 for 8 hours while stirring. After cooling, the resulting precipitate was thoroughly washed with water and then dried at 150 DEG C to obtain scaly flour containing zirconium phosphate. This zirconium phosphate was analyzed and found to be? -Phosphoric zirconium (H type) (hereinafter referred to as? -Phosphoric zirconium (Z2)).

The zirconium? -Phosphate (Z2) was subjected to self-dissolution in nitric acid to which hydrofluoric acid had been added and then subjected to ICP emission spectrometry analysis to obtain the following composition formula.

Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01? 0.05H ₂ O

The median diameter of? -Phosphoric acid zirconium (Z2) was 0.8 占 퐉.

Subsequently, 25 g of? -Phosphoric acid zirconium (Z2) was added with stirring to 1000 mL of 0.1N-LiOH aqueous solution, which was stirred for 8 hours. Thereafter, the precipitate was washed with water and vacuum-dried at 150 ° C for 20 hours to prepare lithium ion-substituted? -Phosphoric zirconium containing Zr _0.99 Hf _0.01 Li _1.03 H _1.00 (PO ₄ ) _2.01 .0.2H ₂ O. The water content by the Karl Fischer method was 0.4%. In this lithium ion-substituted zirconium phosphate, 4 meq / g of all the cation exchange capacity is substituted with lithium ion. Quot; 4meq-Li substituted zirconium a-phosphate A2-1 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-Li substituted zirconium a-phosphate A2-1. The results are shown in Table 1. [

Example 6

The procedure of Example 5 was repeated except that the amount of 0.1N-LiOH aqueous solution was changed to 2500 mL to prepare a solution of Zr _0.99 Hf _0.01 Li _2.03 (all cation exchanger: cation exchange capacity: 6.7 meq / g) PO ₄ ) _2.01 · 0.1H ₂ O was prepared. The moisture content was 0.3%. Hereinafter, &quot; all-Li-substituted? -Phosphoryl zirconium A2-2 &quot;

Subsequently, various evaluations were carried out using the ion trapping material for a solar cell including the entire Li-substituted zirconium? -Phosphate A2-2. The results are shown in Table 1.

Example 7

Instead of 0.1N-LiOH aqueous solution, except that 0.1N-KOH aqueous solution, the embodiment performs the same operation as in Example _{5, Zr 0.99 Hf 0.01 K 1.03} H 1.00 (PO 4) , potassium substituted containing _2.01 · 0.03H ₂ O Type zirconium phosphate was prepared. The water content was 0.5%. In this potassium-substituted? -Phosphate zirconium, 4 meq / g of all the cation exchange capacity are substituted with lithium ions. Quot; 4meq-K substituted zirconium a-phosphate A2-3 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-K-substituted zirconium a-phosphate A2-3. The results are shown in Table 1.

Example 8

The procedure of Example 7 was repeated except that the amount of the aqueous solution of 0.1N-KOH was changed to 2500 mL to prepare a solution of Zr _0.99 Hf _0.01 K _2.03 (product of Kagaku Kogyo Co., Ltd.) in which all the cation exchangers (cation exchange capacity: 6.7 meq / g) PO ₄ ) _2.01 was prepared. The water content was 0.4%. Hereinafter, &quot; all-K-substituted zirconium a-phosphate A2-4 &quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire K-substitution zirconium a-phosphate A2-4. The results are shown in Table 1.

Example 9

The procedure of Example 5 was repeated except that 2500 mL of 0.1 N-Rb ₂ CO ₃ aqueous solution was used in place of the aqueous 0.1 N-LiOH solution, and all the cation exchangers (cation exchange capacity: 6.7 meq / g) were substituted with rubidium ions Rubidium substituted? -Phosphoric zirconium was prepared. The water content was 0.5%. Hereinafter referred to as &quot; entire Rb-substituted? -Phosphoryl zirconium A2-5 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Rb-substituted? -Phosphoric zirconium A2-5. The results are shown in Table 1.

Example 10

The procedure of Example 5 was repeated except that 2500 mL of 0.1N-Cs ₂ CO ₃ aqueous solution was used instead of 0.1N-LiOH aqueous solution, and all the cation exchangers (cation exchange capacity: 6.7 meq / g) were substituted with cesium ions Cesium-substituted zirconium phosphate was prepared. The water content was 0.4%. Hereinafter, &quot; the entire Cs substituted zirconium alpha -phosphate A2-6 &quot;

Subsequently, various evaluations were carried out using the ion trapping material for a solar cell including the entire Cs-substituted zirconium? Zirconium phosphate A2-6, and the results are shown in Table 1.

Example 11

Except that 2500 mL of a 0.1N- (CH ₃ COO) ₂ Mg aqueous solution was used in place of the 0.1N-LiOH aqueous solution, and all of the cation exchangers (cation exchange capacity: 6.7 meq / g) To prepare magnesium-substituted? -Phosphoric zirconium. The water content was 0.5%. Hereinafter referred to as &quot; total Mg-substituted? -Phosphoryl zirconium A2-7 &quot;.

Subsequently, various evaluations were carried out by using the ion trapping material for a solar cell containing the entire Mg-substituted? -Phosphoric zirconium A2-7, and the results are shown in Table 1.

Example 12

Except that 2500 mL of a 0.1N- (CH ₃ COO) ₂ Ca aqueous solution was used instead of the 0.1N-LiOH aqueous solution, and all of the cation exchangers (cation exchange capacity: 6.7 meq / g) Substituted? -Phosphoric zirconium was prepared. The water content was 0.6%. Hereinafter referred to as &quot; total Ca-substituted? -Phosphorylated zirconium A2-8 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Ca-substituted zirconium a-phosphate A2-8. The results are shown in Table 1.

Example 13

To 400 mL of deionized water, 405 g of 75% phosphoric acid was added, and 137 g of titanyl sulfate (content in terms of TiO ₂ : 33%) was added while stirring the aqueous solution. This was refluxed at 100 占 폚 for 48 hours while stirring. After cooling, the resulting precipitate was thoroughly washed with water, and dried at 150 캜 to obtain a scaly flour containing titanium phosphate. As a result of analyzing the titanium phosphate, it was confirmed that it was? -Phosphate (H type).

The above-mentioned? -Phosphate was self-dissolving in nitric acid with addition of hydrofluoric acid and then subjected to ICP emission spectroscopic analysis to obtain the following composition formula.

TiH _2.03 (PO ₄ ) _2.01 · 0.1H ₂ O

Further, the median diameter of the? -Phosphate was measured and found to be 0.7 占 퐉.

Subsequently, 25 g of? -Phosphate was added to 1000 mL of 0.1N-LiOH aqueous solution while stirring, and this was stirred for 8 hours. Then, the precipitate was washed with water and dried at 150 ℃ 20 sigan vacuum to prepare a _{TiLi 1.03 H 1.00 (PO 4)} 2.01 · 0.2H lithium ion substitutional α- titanium phosphate containing O _2. The water content was 0.5%. This lithium ion-substituted? -Phosphate is obtained by substituting 4 meq / g of lithium ions for all the cation exchange capacity. Quot; 4meq-Li substituted? -Phosphate titanium B-1 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-Li substituted titanium phosphate B-1, and the results are shown in Table 1.

Example 14

0.1N-LiOH, except that the amount of the aqueous solution to 2500mL, Example 13 and subjected to the same operation, any cation-exchange (cation exchange capacity: 7.0meq / g) is substituted by lithium ion, TiLi _2.03 (PO _{4) 2.01} A lithium ion-substituted? -Phosphate containing 0.1H ₂ O was prepared. The water content was 0.4%. Hereinafter referred to as &quot; total Li-substituted? -Phosphate titanium B-2 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for a solar cell including the entire Li-substituted type? -Phosphate B-2, and the results are shown in Table 1.

Example 15

Instead of 0.1N-LiOH aqueous solution, 0.1N-KOH aqueous solution was used, is performed in the same manner as in Example _{13, TiK 1.03 H 1.00 (PO} 4) 2.01 · 0.05H type potassium ion substituted ₂ O containing α- Titanium phosphate was prepared. The water content was 0.4%. Quot; 4meq-K-substituted? -Phosphate titanium B-3 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the 4meq-K-substituted? -Phosphate titanium B-3, and the results are shown in Table 1.

Example 16

0.1N-KOH, except that the amount of the aqueous solution to 2500mL, performed in the same manner as in Example 13, all of cation exchange groups: the (cation exchange capacity of 7.0meq / g) is replaced with potassium ions, TiK _2.03 (PO _{4) 2.00} Of potassium-substituted &lt; RTI ID = 0.0 &gt; a-phosphate &lt; / RTI &gt; The water content was 0.5%. Hereinafter referred to as &quot; all-K-substituted? -Phosphate titanium B-4. &Quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire K-substitution type? -Phosphate B-4, and the results are shown in Table 1.

Example 17

The procedure of Example 13 was repeated except that 2500 mL of 0.1 N-Rb ₂ CO ₃ aqueous solution was used instead of 0.1 N-LiOH aqueous solution, and all the cation exchangers (cation exchange capacity: 7.0 meq / g) were substituted with rubidium ions Rubidium substituted? -Phosphate was prepared. The water content was 0.4%. Hereinafter, &quot; total Rb-substituted? -Phosphate titanium B-5 &quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Rb-substituted? -Phosphate titanium B-5, and the results are shown in Table 1.

Example 18

The procedure of Example 13 was repeated except that 2500 mL of 0.1 N-Cs ₂ CO ₃ aqueous solution was used instead of 0.1 N-LiOH aqueous solution, and all cation exchangers (cation exchange capacity: 7.0 meq / g) were substituted with cesium ions Cesium-substituted? -Phosphate was prepared. The water content was 0.5%. Hereinafter, &quot; total Cs-substituted? -Phosphate titanium B-6 &quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Cs-substituted type? -Phosphate B-6. The results are shown in Table 1.

Example 19

Except that 2500 mL of 0.1 N - (CH ₃ COO) ₂ Mg aqueous solution was used in place of 0.1 N - LiOH aqueous solution, and all the cation exchangers (cation exchange capacity: 7.0 meq / g) To prepare magnesium-substituted? -Phosphate. The water content was 0.5%. Hereinafter referred to as &quot; total Mg-substituted? -Phosphate titanium B-7 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for a solar cell containing the entire Mg-substituted? -Phosphate B-7, and the results are shown in Table 1.

Example 20

(Cation exchange capacity: 7.0 meq / g) was used in place of the 0.1 N - (CH ₃ COO) ₂ Ca aqueous solution in place of the 0.1 N - (CH ₃ COO) ₂ Ca aqueous solution, Substituted? -Phosphate was prepared. The water content was 0.4%. Hereinafter referred to as &quot; total Ca-substituted? -Phosphate titanium B-8 &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Ca-substituted type? -Phosphate B-8, and the results are shown in Table 1.

Example 21

The entire Li-substituted zirconium salt of? -Phosphoric acid A1-2 and the entire K-substituted zirconium salt of? -Phosphoric acid A1-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. The above-mentioned various evaluations were carried out, and the results are shown in Table 1.

Example 22

The entire Li-substituted zirconium salt of? -Phosphoric acid A1-2 and the entire Li-substituted zirconium salt of? -Phosphoric acid A2-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. The above-mentioned various evaluations were carried out, and the results are shown in Table 1.

Example 23

The entire Li-substituted zirconium salt of? -Phosphoric acid A1-2 and the entire K-substituted zirconium salt of? -Phosphoric acid A2-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. The above-mentioned various evaluations were carried out, and the results are shown in Table 1.

Example 24

The entire Li-substituted zirconium salt of? -Phosphoric acid A1-2 and the entire Li-substituted? -Phosphate B-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. The above-mentioned various evaluations were carried out, and the results are shown in Table 1.

Example 25

The entire Li-substituted zirconium salt of? -Phosphoric acid A1-2 and the entire K-substituted type of? -Phosphate B-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 26

The entire K-substituted zirconium? -Phosphate A1-4 and the entire Li-substituted? -Zirconium zirconium A2-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 27

The entire K-substituted zirconium salt of? -Phosphoric acid A1-4 and the entire K-substituted type of zirconium salt of? -Phosphoric acid A2-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 28

The entire K-substituted zirconium? -Phosphate A1-4 and the entire Li-substituted? -Phosphate B-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 29

The entire K-substitutional zirconium a-phosphate A1-4 and the entire K-substituted α-phosphate titanium B-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 30

The entire Li-substituted zirconium salt of? -Phosphoric acid A2-2 and the entire K-substituted zirconium salt of? -Phosphoric acid A2-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 31

The entire Li-substituted zirconium salt of? -Phosphoric acid A2-2 and the entire Li-substituted? -Phosphate B-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 32

The entire Li-substituted α-zirconium phosphate zirconium A2-2 and the entire K-substituted α-phosphate titanium B-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 33

The entire K-substituted zirconium a-phosphate A2-4 and the entire Li-substituted? -Phosphate B-2 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 34

The entire K-substitutional zirconium? -Phosphate A2-4 and the entire K-substituted? -Phosphate B-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Example 35

The entire Li-substituted? -Phosphate B-2 and the entire K-substituted? -Phosphate B-4 were mixed at a mass ratio of 1: 1 to obtain an ion trapping agent for a solar cell. Then, various evaluations as described above were carried out, and the results are shown in Table 2.

Comparative Example 1

The inorganic ion exchanger "IXE100" (trade name) manufactured by Toagosei Co., Ltd., which is α-phosphate zirconium (H type), which was not substituted with a cation, was used as it was and various evaluations were carried out. The results are shown in Table 2.

Comparative Example 2

Instead of 0.1N-LiOH aqueous solution, 0.1N-NaOH, except that there was used an aqueous solution of 2500mL, the embodiment performs the same operation as in Example 5, all the cation-exchange (cation exchange capacity: 6.7meq / g) is replaced by a sodium ion, Zr _0.99 Sodium substituted? -Phosphoric zirconium containing Hf _0.01 Na _2.03 (PO ₄ ) _2.01? 0.05H ₂ O was prepared. The water content was 0.5%. Hereinafter, &quot; total Na-substituted? -Phosphate zirconium &quot;

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Na-substituted type? -Phosphate zirconium, and the results are shown in Table 2.

Comparative Example 3

The α-phosphate (H-form) prepared in Example 13 was used as it was and various evaluations were carried out. The results are shown in Table 2.

Comparative Example 4

The procedure of Example 13 was repeated except that 2500 mL of 0.1 N NaOH aqueous solution was used in place of 0.1 N-LiOH aqueous solution, and TiNa _2.03 (trade name) was used in which all the cation exchangers (cation exchange capacity: 7.0 meq / g) (PO ₄ ) _2.00 · 0.05H ₂ O was prepared. The water content was 0.5%. Hereinafter referred to as &quot; total Na-substituted? -Phosphate titanium &quot;.

Subsequently, various evaluations were carried out using the ion trapping agent for solar cells containing the entire Na-substituted type? -Phosphate. The results are shown in Table 2.

Comparative Example 5

Y type zeolite &quot; Mizuka Seabus Y-520 &quot; (trade name) manufactured by Mizusawa Chemical Co., Ltd. was dried at 150 DEG C for 20 hours, and various evaluations were performed. The results are shown in Table 2.

It can be seen from Tables 1 and 2 that the ion trapping agent for solar cells of Examples 1 to 35 has a high capture ratio of Na ⁺ ions in the NaCl aqueous solution and the pH fluctuation is within 1. Also, in the extracted water after immersing the crosslinked resin test piece in pure water, the ion trapping agents for solar cells of Examples 1 to 35 showed a high dissolution inhibiting performance of Na ⁺ ions. From these results, it was found that the ion trapping agent of the present invention adsorbs Na ⁺ ions, which are considered to be the cause of PID of the solar cell, and does not cause deterioration of the pH, Can be suppressed.

The ion trapping agent for a solar cell of the present invention selectively adsorbs Na ⁺ ions that cause PID of the solar cell and is difficult to release H ⁺ ions, so that the sealing layer constituting the solar cell module, And the like. Thus, a solar cell having excellent durability can be formed. It is also possible to add it to the silver electrode paste or the like.

The present invention relates to a solar cell module, a solar cell module, a solar cell module, a sealing layer,

Claims (8)

(A) zirconium phosphate in which at least a part of the ion exchanger is substituted with at least one ion (a1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion, and (B) Characterized in that at least a part of the? -Phosphorus compound contains at least one of? -Phosphate substituted with at least one ion (b1) selected from lithium ion, potassium ion, cesium ion, rubidium ion, magnesium ion and calcium ion Ion trapping agent. The ion trap agent for a solar cell according to claim 1, wherein the component (A) is? -Phosphoric acid zirconium substituted with the ion (a1) in an amount of 0.1 to 6.7 meq / g in the total ion exchange capacity. The ion trapping material for a solar cell according to claim 1 or 2, wherein the? -Phosphoric zirconium before substitution with the ion (a1) is a compound represented by the following formula (1).
_{Zr 1-x Hf x H a} (PO 4) b · mH 2 O (1)
(Wherein 0? X? 0.2, 2 < b? 2.1 and a is a number satisfying 3b-a = 4 and 0? M? 2) 4. The solar cell according to any one of claims 1 to 3, wherein the component (B) is an? -Phosphate in which 0.1 to 7.0 meq / g of the total ion exchange capacity is replaced with the ion (b1) My. The ion trap agent for a solar cell according to any one of claims 1 to 4, wherein the? -Phosphate before substitution with the ion (b1) is a compound represented by the following formula (2).
_{TiH s (PO 4) t ·} nH 2 O (2)
(Where 2 < t &lt; = 2.1 and s is a number satisfying 3t-s = 4 and 0 & An encapsulant composition for a solar cell, comprising the ion trapping agent for a solar cell according to any one of claims 1 to 5 and a resin. The encapsulating composition for a solar cell according to claim 6, wherein the resin comprises an ethylene / vinyl acetate copolymer resin. The solar cell element according to any one of claims 6 to 7, further comprising a solar cell element, a front surface side transparent protective member, a back surface side protective member, and a front surface side transparent protective member and a back surface side protective member, A solar cell module comprising a sealing layer sealed using an encapsulant composition.

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