KR101860651B1 - Solar cell encapsulant EVA sheet - Google Patents

Solar cell encapsulant EVA sheet Download PDF

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KR101860651B1
KR101860651B1 KR1020160178353A KR20160178353A KR101860651B1 KR 101860651 B1 KR101860651 B1 KR 101860651B1 KR 1020160178353 A KR1020160178353 A KR 1020160178353A KR 20160178353 A KR20160178353 A KR 20160178353A KR 101860651 B1 KR101860651 B1 KR 101860651B1
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sheet
solar cell
tert
eva
metal ion
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한재혁
박지용
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한화토탈 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
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    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The present invention relates to a solar cell encapsulant EVA sheet that has excellent anti-potential induced degradation (PID) characteristics. According to the present invention, the solar cell encapsulant EVA sheet, which has an EVA resin, includes: the EVA resin having 23 to 29 weight% of vinyl acetate and a melting index of 5 to 30g/10 min, wherein the EVA sheet has at least two layers. A solar cell comes into contact with one surface of any one of the at least two layers. Only a sheet, which comes into contact with the solar cell, includes a metal ion absorbing agent. A sheet, which does not come into contact with the solar cell, does not include the metal ion absorbing agent. The sheet including the metal ion absorbing agent has a thickness corresponding to 2 to 15% of the entire thickness of the EVA sheet. 200 to 2000 ppm of the metal ion absorbing agent is included in only a layer contacting a cell. The solar cell encapsulant EVA sheet is used in a light receiving unit of a solar cell module. The solar cell encapsulant EVA sheet does not make loss in sunlight transmittance and effectively absorbs Na ions. 200 to 2000 ppm of an acetic acid degradation repression component is dispersed in the entire sheet to repress generation of glass acetic acid and suppress movement of Na ions.

Description

EVA sheet for solar cell encapsulant {Solar cell encapsulant EVA sheet}

The present invention relates to an ethylene vinyl acetate (EVA) sheet used for a solar cell encapsulant, which protects a cell of a solar cell from external impact when used in a solar cell module and satisfies a required solar transmittance And a method for manufacturing an EVA sheet for securing electrical insulation. EVA has been widely used for many years as a bar material for photovoltaic modules due to its high transparency and ease of processing, long-term durability and cost advantages. However, recently, some cell types are found to be vulnerable to PID phenomenon when EVA encapsulant is used. PID (Potential Induced Degradation) phenomenon is a phenomenon of power generation efficiency deterioration. When the solar module is exposed to high temperature and high humidity environment, the insulation is drastically deteriorated due to the high voltage (high potential) applied to the module, . ≪ / RTI > Efforts are being made to improve anti-PID cells and sealing materials to overcome such PID phenomenon. The present invention relates to a method of manufacturing an EVA sheet for alleviating such a PID phenomenon and an EVA sheet produced by the method.

The photovoltaic module consists of a cell that produces electricity, an encapsulating material on both sides, a front glass part that receives sunlight, and a back sheet that has moisture and gas barrier function. In order to prevent the loss of sunlight transmittance, the encapsulant should be made as transparent as possible. For this purpose, EVA resin will be used with the highest amount of vinyl acetate (VA, vinyl acetate). However, the increase in transparency with increasing VA content does not show any significant difference from 30%. The higher the VA content, the worse the electrical insulation becomes and the viscosity increases and the processing becomes difficult. On the other hand, when the content of vinyl acetate is low, blocking of the sheet, low vapor transmissivity, and excellent electrical insulation are poor, but transparency and adhesiveness are poor. To overcome this disadvantage, various additives are required to be excessively prescribed .

Meanwhile, PID phenomenon, which is a problem in recent years, is considered to be related to the electrical characteristics and degradation characteristics of EVA. The PID phenomenon is caused by the polarization phenomenon in the cell due to the leakage current to the module and the outside due to the high voltage or the reduction of the shunt resistance in the emitter layer due to the migration of Na ions separated from the glass to the cell surface . The leakage current is related to the insulation property of the EVA encapsulant responsible for the electrical insulation of the cell. As a method for solving the problem in this respect, Korean Patent Laid-Open No. 10-2014-0090340 proposes EVA encapsulant additives, A method of increasing the electrical insulation resistance value of the battery is proposed. Japanese Laid-Open Patent Application No. 2014-150246 also discloses a method of prescribing an additive containing Na adsorption function as a method for suppressing Na migration. On the other hand, EVA is known to decompose VA at high temperature by moisture to generate acetic acid. It is known that acetic acid generated by inducing corrosion of glass induces Na ion generation and also helps liberation of Na ion. A method of adding acetic acid reactive additive is proposed as a solution for the problem. However, in the case of an increase in the amount of additives or in the case of an additional formulation, discoloration of the color due to the deterioration of the additive itself (increase in the yellow index) is caused. In addition, Which has a problem of reducing sunlight.

Therefore, development of an EVA sheet for a solar cell encapsulant that does not cause problems in the long-term performance of the solar module and the member and which can mitigate the PID phenomenon without lowering the light transmittance is required.

An object of the present invention to solve the above problems is to provide an EVA sheet for a solar cell encapsulant excellent in anti-PID (Potential Induced Degradation) characteristics, which effectively disperses a metal ion adsorbent on an EVA sheet without impairing light transmittance, The decomposition inhibitor is to provide an EVA sheet for a solar cell encapsulant which can maximize the effect without side reaction and overcome the PID phenomenon.

According to an aspect of the present invention,
1. An EVA sheet for a solar cell encapsulant comprising an EVA resin,
The EVA resin has a vinyl acetate content of 23 to 29 wt% and a melt index of 5 to 30 g / 10 min (190 DEG C, 2.16 kg of ASTM D1238)
Wherein the EVA sheet for a solar cell encapsulant comprises at least two or more multi-
Wherein at least one of the two or more multi-layered sheets is in contact with the solar cell, and only the sheet in contact with the solar cell out of the multi-layered sheets includes a metal ion adsorbent,
Wherein the sheet not contacting the solar battery cell among the sheets of the multi-layer structure does not contain the metal ion adsorbent,
The sheet containing the metal ion adsorbent is 2 to 15% of the total thickness of the multi-layered sheet,
The metal ion adsorbent is contained in an amount of 200 to 2000 ppm,
Wherein the multi-layer structure sheet contains the nitric decomposition inhibitor in an amount of 200 to 2000 ppm,

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The acetic acid decomposition inhibitor is Carbodiimide represented by the following Chemical Formula 1 or 2,

Wherein the metal ion adsorbent is selected from the group consisting of a bismuth oxide ion adsorbing agent, an antimony oxide ion adsorbing agent, a titanium phosphate ion adsorbing agent, a zirconium phosphate ion adsorbing agent represented by the following Chemical Formulas 4 to 6, Wherein the EVA sheet is at least one selected from the group consisting of aluminum oxide-based ionic adsorbents and aluminum silicate-based ionic adsorbents.

≪ Formula 1 >

RN = C = NR

(Wherein R is an alkyl group having 1 to 4 carbon atoms)

(2)

R (N = C = NR) n

(Wherein R is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 1000)

(3)

BiO X (OH) Y (NO 3) Z

(Wherein x is an integer or a prime number of 0.9 to 1.1, Y is a prime number of 0.6 to 0.8, and Z is a prime number of 0.2 to 0.4)

≪ Formula 4 >

Zr [HPO 4 ] 2 H 2 O

≪ Formula 5 >

Ti [HPO 4 ] 2 H 2 O

(6)

Zr 1 - x Tix [HPO 4 ] 2 H 2 O

(Where x is a prime number of 0.25 to 0.75)

≪ Formula 7 >

Al 2 O 3 .3SiO 2

INDUSTRIAL APPLICABILITY The EVA sheet for a solar cell encapsulant of the present invention effectively prevents migration and deposition of cells, which cause PID phenomenon, effectively prevents loss of sunlight transmittance and effectively decomposes acetic acid, Excellent durability.

1 is a graph showing a solar light transmittance according to an embodiment of the present invention.
2 is a graph illustrating a PID (Potential Induced Degradation) according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides an EVA sheet for a solar cell encapsulant comprising an EVA resin,
The EVA resin has a vinyl acetate content of 23 to 29 wt% and a melt index of 5 to 30 g / 10 min (190 DEG C, 2.16 kg of ASTM D1238)
Wherein the EVA sheet for a solar cell encapsulant comprises at least two or more multi-
Wherein at least one of the two or more multi-layered sheets is in contact with the solar cell, and only the sheet in contact with the solar cell out of the multi-layered sheets includes a metal ion adsorbent,
Wherein the sheet not contacting the solar battery cell among the sheets of the multi-layer structure does not contain the metal ion adsorbent,
The sheet containing the metal ion adsorbent is 2 to 15% of the total thickness of the multi-layered sheet,
The metal ion adsorbent is contained in an amount of 200 to 2000 ppm,
Wherein the multi-layer structure sheet contains the nitric decomposition inhibitor in an amount of 200 to 2000 ppm,
The acetic acid decomposition inhibitor is Carbodiimide represented by the following Chemical Formula 1 or 2,

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delete

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Wherein the metal ion adsorbent is selected from the group consisting of a bismuth oxide ion adsorbing agent, an antimony oxide ion adsorbing agent, a titanium phosphate ion adsorbing agent, a zirconium phosphate ion adsorbing agent represented by the following Chemical Formulas 4 to 6, And an aluminum silicate ion-adsorbing agent. The present invention also relates to an EVA sheet for a solar cell encapsulant.

≪ Formula 1 >

RN = C = NR

(Wherein R is an alkyl group having 1 to 4 carbon atoms)

(2)

R (N = C = NR) n

(Wherein R is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 1000)

(3)

BiO X (OH) Y (NO 3) Z

(Wherein x is an integer or a prime number of 0.9 to 1.1, Y is a prime number of 0.6 to 0.8, and Z is a prime number of 0.2 to 0.4)

≪ Formula 4 >

Zr [HPO 4 ] 2 H 2 O

≪ Formula 5 >

Ti [HPO 4 ] 2 H 2 O

(6)

Zr 1 - x Tix [HPO 4 ] 2 H 2 O

(Where x is a prime number of 0.25 to 0.75)

≪ Formula 7 >

Al 2 O 3 .3SiO 2

In the present invention, the EVA sheet for the solar cell encapsulant may include an EVA resin, a metal ion adsorbent, and a nitric decomposition inhibitor.

The EVA resin may have a vinyl acetate content of 23 to 29 wt%, and preferably has a melt index of 5 to 30 g / 10 min (190 DEG C, 2.16 kg of ASTM D1238).

If the VA content is less than 23% by weight, the transparency is lowered, and the sunlight transmittance is lowered and the adhesive strength is lowered, which is undesirable. When the VA content is more than 29% by weight, decomposition of the vinyl acetate functional group is promoted and the content of free acetic acid increases sharply .

If the melt index of the EVA resin is less than 5 g / 10 min, the productivity of the extruder is increased due to an increase in pressure of the extruder during sheet processing. If the melt index exceeds 30 g / 10 min, It is not preferable because leakage increases to the outside of the module or causes movement of the solar battery cell.

In the present invention, the EVA sheet for the solar cell encapsulant may be made of at least two or more multi-layered sheets by double layer co-extrusion, and the solar cell may be contacted to one surface of the multi-layered sheet.

The sheet to be contacted with the solar cell may include a metal ion adsorbent, and the acetic acid decomposition inhibitor may be included in the entire EVA sheet.

The metal ion adsorbent is preferably included only in the layer contacting the solar cell, and is preferably contained in an amount of 200 to 2000 ppm.

If the metal ion adsorbent is included only in the layer in contact with the solar cell, it can exhibit a very excellent functional effect around the solar cell cell rather than being dispersed throughout the EVA sheet.

The EVA sheet is composed of two or more multi-layer sheets, and the additives other than the metal ion adsorbent contained in the layer in contact with the solar cell can be added in the same composition without discrimination of layers.

The thickness of the sheet containing the metal ion adsorbent is preferably 2 to 15% of the total thickness of the multi-layered sheet. If the thickness of the sheet containing the metal ion adsorbent is less than 2% If it exceeds 15%, there is a problem that the solar light transmittance is significantly lowered.

In the present invention, it is preferable that the metal ion adsorbent is contained only in a layer which is contacted with a solar battery cell as a Na ion adsorbent, and may be contained at 200 to 2000 ppm, preferably 500 to 1000 ppm.

If the metal ion adsorbent is contained in an amount of less than 200 ppm, the metal ion adsorption effect is insignificant. If the metal ion adsorbent is contained in an amount exceeding 2,000 ppm, light scattering increases and cell efficiency is lowered.

In the present invention, the nitric acid decomposition inhibitor is carbodiimide or polycarbodiimide, and is preferably contained at 200 to 2,000 ppm, more preferably 500 to 1,000 ppm.

If the acetic acid decomposition inhibitor is contained in an amount of less than 200 ppm, the effect of inhibiting the formation of acetic acid is insignificant. If the acetic acid decomposition inhibitor is contained in an amount exceeding 2,000 ppm, discoloration may occur.

The acetic acid decomposition inhibitor is preferably a carbodiimide compound represented by the following formula (1) or (2), and a monomer type and an oligomer type may be used.

≪ Formula 1 >

RN = C = NR

(Wherein R is an alkyl group having 1 to 4 carbon atoms)

(2)

R (N = C = NR) n

(Wherein R is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 1000)

In the present invention, the metal ion adsorbent is an inorganic compound having an ion-adsorbing ability, such as a phosphate anion, a phosphite anion, an organic acid anion, an alkali metal cation-containing compound, an alkaline earth metal cation- At least one selected from an adsorbent, a titanium phosphate ion adsorbent, a zirconium phosphate ion adsorbent, and an aluminum silicate ion adsorbent is preferable.

The bismuth oxide-based ionic adsorbent and the antimony oxide-based ionic adsorbent may be represented by the following formula (3).

(3)

BiO X (OH) Y (NO 3) Z

(Wherein X is an integer or a prime number of 0.9 to 1.1, Y is a prime number of 0.6 to 0.8, and Z is a prime number of 0.2 to 0.4)

The titanium phosphate ion adsorbent and the zirconium phosphate ion adsorbent may be represented by any one of the following formulas (4) to (6).

≪ Formula 4 >

Zr [HPO 4 ] 2 H 2 O

≪ Formula 5 >

Ti [HPO 4 ] 2 H 2 O

(6)

Zr 1 - x Tix [HPO 4 ] 2 H 2 O

(Where x is a prime number of 0.25 to 0.75)

The aluminum silicate ion adsorbent may be represented by the following general formula (7).

≪ Formula 7 >

Al 2 O 3 .3SiO 2

In the present invention, the EVA sheet may include at least one selected from crosslinking agents and crosslinking aids for proper crosslinking and adhesion at the time of lamination for manufacturing a module, and EVA sheet processing for long-term stability.

The crosslinking agent is preferably at least one selected from the group consisting of peroxyketals having a half-life of 1 hour at 110 to 120 ° C, peroxycarbonates having a half-life of 1 hour at 90 to 130 ° C and dialkyl peroxides having a half-life of 1 hour at 130 to 150 ° C .

The peroxyketals may be selected from the group consisting of 1,1-di (tert-amylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, -Butylperoxy) cyclohexane, and the peroxycarbonate is 2,5-dimethyl-2,5-di- (2-ethylhexanonylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, tert- Butyl peroxy-2-ethyl hexanoate, tert-amyl (2-ethylhexyl) monoperoxycarbonate, tert-butyl isopropyl monoperoxycarbonate, 2,5-dimethyl- ) Hexane, tert-butyl- (2-ethylhexyl) monoperoxycarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl peroxybenzoate, and the dialkyl peroxide is selected from the group consisting of dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) Peroxy) diisopropylbenzene, di-tert-amyl peroxide, di-tert- Tilpeo oxide, a 2,5-dimethyl--2-5- di (tert- butylperoxy) hexyne-3.

If the content of the crosslinking agent is less than 0.1 part by weight, sufficient crosslinking can not be attained. When the amount of the crosslinking agent is more than 1.5 parts by weight, bubbles may be formed at the time of lamination Unreacted cross-linking agent remains and may affect long-term properties, which is not preferable.

The EVA sheet using the ethylene vinyl acetate copolymer resin composition of the present invention may include a crosslinking aid together with a crosslinking agent.

The crosslinking assistant may be at least one selected from the group consisting of polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate and the like, ethylene glycol diacrylate, ethylene glycol dimethacrylate and trimethyl And polypropane trimethacrylate.

The content of the crosslinking aid is preferably 0.1 to 1.5 parts by weight based on 100 parts by weight of the total composition.

If the amount of the crosslinking aid is less than 0.1 part by weight, the target crosslinking degree will not be satisfied. If the amount is more than 1.5 parts by weight, the crosslinking degree is too high, so that the stress applied to the cell may not be effectively removed. .

The EVA sheet for a solar cell using the ethylene vinyl acetate copolymer resin composition of the present invention may further contain various other additives as necessary.

Specifically, the additive is preferably an ultraviolet absorber, a UV stabilizer, a silane coupling agent, a hindered phenol-based or phosphite-based antioxidant, a hindered amine-based UV stabilizer, a UV absorber, a flame retardant or a discoloration inhibitor.

Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 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- 4,4'-dimethoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone, and the content of the ultraviolet absorber is 0.05 to 0.5 By weight.

Examples of the ultraviolet stabilizer include bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate, bis-1-methyl-2,2,6,6-tetramethyl- (2'-hydroxy-3 ', 5'-ditertbutylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di- tert -amylphenyl) -2H-benzotriazole And poly (methylpropyl) -3-oxo- (4 (2,2,6,6-tetramethyl-4-piperidinyl) siloxane, and the content of the ultraviolet stabilizer is 100 parts by weight By weight based on the total weight of the composition.

The silane coupling agent may be used to improve the adhesion between the EVA sheet and the glass or the cell. Specific examples thereof include? -Methacryloxypropyltrimethoxysilane, N- (? -Aminoethyl) -? - aminopropyl May be at least one member selected from trimethoxysilane, N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane,? -Aminopropyltriethoxysilane and? -Glycidoxypropyltrimethoxysilane , The content of the silane coupling agent is preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the total composition.

The additives may be dry blended into an ethylene vinyl acetate copolymer resin and fed into an extruder or side fed with an extruder separately from EVA.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples.

Sheet Manufacturing Conditions

The extruder temperature was set to 100 DEG C in a single screw extruder having a T-die width of 400 mm with two extruders having a screw diameter of 40 mm, and the rotational speed of each screw was adjusted to adjust the thickness ratio of each layer Thereby preparing a multilayer solar cell EVA sheet having an adjusted total thickness of 450 mu m.

How to measure property

The physical properties of the prepared EVA resin were measured by the following methods and standards.

1) Light transmittance: The light transmittance in the range of 900 to 200 nm was measured using a UVvis-spectrometer. The sample was prepared by putting the sheet produced in the extruder described below between two sheets of low iron glass for solar light and then lamination at 150 ° C.

2) Volumetric intrinsic resistivity (electrical insulation): It was measured according to ASTM D257 (Voltage is 1,000V) using an electric resistance meter.

3) Acetic acid production: 1 g of sheet was placed in a vial with 10 ml of water, sealed, and placed in an oven at 85 ° C. After 1000 hours, acetic acid production was measured by Ion Chromatograph (I C).

4) Measurement of YI: The prepared EVA sheet was sandwiched between low-iron glass for solar light and back white back sheet for solar cell, laminated at 150 ° C to prepare a sample, and after a lapse of 1000 hours at 85 ° C and 85 RH, And the YI (yellow index) was measured.

5) PID (Potential Induced Degradation) measurement: Mini module was manufactured using 4 Si single crystals and manufactured EVA sheets. The IV curve was drawn using a solar simulator and the initial Power_max value was obtained. After holding for 96 hours under 1000V voltage application, Power_max value was measured after the test using Solar simulator to calculate the power production maintenance rate.

Example  One

Ethylenevinyl acetate copolymer (Hanwha Total E285PV) having a melt index (190 DEG C, 2.16 Kg) of 7 g / 10 min and a vinyl acetate content of 26% by mass was charged with Alchemas Luperox TBEC (tert-butyl-2-ethylhexyl monoperoxycarbonate) , 0.5 part by weight of TAICROS (triallyl isocyanurate) from Ebonics as a crosslinking aid, 0.2 parts by weight of Chimassorb 81 (2-hydroxy-4-octyloxy-benzophenone) 0.1 part by weight of Tinuvin 770 (bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate) from Rosiba Corporation, OFS 6030 from Dow Corning Corporation as a silane coupling agent (? -Methacryloxypropyl trimethylene Methoxy silane) were commonly mixed.

 Also, 1000 ppm of Carbodiimide (product name: Staboxol P 100, product of Rhein Chemie) was mixed as an acetic acid generation inhibiting component. In the side extruder, 1000 ppm of zirconium phosphate compound (Zr [HPO 4] 2 H 2 O) was added in addition to the above additives, and then sheets were produced through an extruder.

The rpm of the extruder for extruding the EVA resin layer containing zirconium phosphate as a metal ion adsorbent was adjusted to 1/20 of the rpm of the main extruder so that the thickness ratio was adjusted to 5% of the total layer. The extruder temperature and the T-die temperature were maintained at 100 ° C and an EVA sheet for a solar module with a thickness of 450 μm was produced.

The specimens were prepared by the method described in the physical property measurement method of the EVA sheet, and then physical properties were measured according to each item. The measurement results are summarized in Table 1 below.

Example  2

In Example 1, the rpm of the side extruder was adjusted to 1/19 of the rpm of the main extruder to adjust the thickness of the Na ion adsorbent-containing layer to 10% and the content of Carbodiimide to 500 ppm. .

Example  3

The procedure of Example 1 was repeated except that the rpm of the side extruder was adjusted to 1/9 of the rpm of the main extruder to adjust the thickness of the Na ion adsorbent-containing layer to 10%.

Comparative Example  One

Example 1 was prepared in the same manner as in Example 1, except that the Na ion adsorbent was not injected to prepare an EVA sheet as a single layer without discrimination of layers.

Comparative Example  2

The procedure of Example 1 was repeated except that the Na ion adsorbent was changed to 100 ppm in Example 1.

Comparative Example  3

The procedure of Example 1 was repeated except that the Na ion adsorbent was changed to 5000 ppm in Example 1.

Comparative Example  4

The procedure of Example 1 was repeated except that the rpm of the side extruder in Example 1 was adjusted to 3/7 of the rpm of the main extruder to adjust the thickness of the Na ion adsorbent containing layer to 30%.

Comparative Example  5

Example 1 was prepared in the same manner as in Example 1, except that 1000 ppm of Na ion adsorbent was also injected into the EVA injected into the main extruder, so that the Na ion adsorbent was distributed throughout the sheet without discriminating the layers.

Comparative Example  6

Example 2 was prepared in the same manner as in Example 2, except that Carbodiimide was not injected.

Comparative Example  7

The procedure of Example 2 was repeated except that the content of Carbodiimide was increased to 3000 ppm in Example 2.

Example Comparative Example One 2 3 One 2 3 4 5 6 7 Na ion capture
(ppm) 1000 1000 1000 - 100 5000 1000 1000 1000 1000 Na ion adsorbent layer thickness ratio (%) 5 10 10 0 5 5 30 100 10 10 CDI content (ppm) 1000 500 1000 1000 1000 1000 1000 1000 - 3000 Light transmittance%
(400 to 750 nm) 90.2 90.1 89.8 90.4 90.2 81.8 77.5 70.1 89.7 88.0 Volume resistivity
Early
(Ω.cm) * 10 ^ 15 3.54 4.62 5.48 1.52 1.56 5.23 4.85 5.36 2.35 2.56 Volume resistivity
1000hr elapsed
(Ω.cm) * 10 ^ 15 1.45 2.23 3.58 0.45 0.51 4.26 1.84 2.87 0.73 0.98 Acetic acid production
1000 h elapsed (ppm) 125 131 120 156 150 105 117 138 352 8 Acetic acid production
2000hr elapsed 250 262 245 280 273 211 190 182 674 23 Acetic acid production
3000hr elapsed 330 380 300 450 350 180 280 250 1200 50 PID output initial value (W) 16.5 16.3 14.8 16.3 16.3 16.2 16.2 16.2 16.4 14.6 PID output end value (W) 15.9 16.0 14.7 12.9 13.1 15.1 15.4 15.6 13.5 12.9 Output retention rate (%) 97 98 100 79 80 88 95 96 82 93 ? YI (1000 hr) 1.2 1.1 1.3 1.3 1.2 1.3 1.4 1.5 1.1 3.6

As shown in Table 1, in the case of Comparative Example 1 which does not contain the Na ion adsorbent according to Examples 1 to 3 of the present invention, the output rapidly decreases after the PID test, and the power retention rate is only 79%.

In the case of Comparative Example 2 in which the content of Na ion adsorbent is low, it is understood that the output retention rate is similar to 80% as in Comparative Example 1.

In addition, in Comparative Example 3 in which the Na ion adsorbent content is as high as 5000 ppm, the light transmittance is as low as 81.8%, which indicates that the performance as a solar module can not be exhibited properly.

In Comparative Example 4 in which the thickness of the Na ion adsorbent-containing layer is 30% and in Comparative Example 5 in which the total thickness is 100%, the light transmittance is very low due to scattering of the adsorbent.

In the case of Comparative Example 6 in which no carbodiimide was added, the amount of acetic acid generated was very high, and thus the volume resistivity value was extremely lowered after the Damp Heat 1000 hr, and even when the Na ion adsorbent contained an appropriate level of the Na ion adsorbent, It can be seen that it can not be done.

In the case of Comparative Example 7 in which the nitric oxide decomposition inhibitor content is 3000 ppm, the yellowing proceeds after 1000 hours of Damp Heat due to the degradation of the additive itself, so that the value of? Y.I is greatly increased.

Claims (9)

1. An EVA sheet for a solar cell encapsulant comprising an EVA resin,
The EVA resin has a vinyl acetate content of 23 to 29 wt% and a melt index of 5 to 30 g / 10 min (190 DEG C, 2.16 kg of ASTM D1238)
Wherein the EVA sheet for a solar cell encapsulant comprises at least two or more multi-
Wherein at least one of the two or more multi-layered sheets is in contact with the solar cell, and only the sheet in contact with the solar cell out of the multi-layered sheets includes a metal ion adsorbent,
Wherein the sheet not contacting the solar battery cell among the sheets of the multi-layer structure does not contain the metal ion adsorbent,
The sheet containing the metal ion adsorbent is 2 to 15% of the total thickness of the multi-layered sheet,
The metal ion adsorbent is contained in an amount of 200 to 2000 ppm,
Wherein the multi-layer structure sheet contains the nitric decomposition inhibitor in an amount of 200 to 2000 ppm,
Wherein the nitric acid decomposition inhibitor is Carbodiimide represented by the following formula (1) or (2)
Wherein the metal ion adsorbent is selected from the group consisting of a bismuth oxide ion adsorbing agent, an antimony oxide ion adsorbing agent, a titanium phosphate ion adsorbing agent, a zirconium phosphate ion adsorbing agent represented by the following Chemical Formulas 4 to 6, Wherein said EVA sheet is at least one selected from the group consisting of aluminum silicate ion adsorbents.
≪ Formula 1 >
RN = C = NR
(Wherein R is an alkyl group having 1 to 4 carbon atoms)
(2)
R (N = C = NR) n
(Wherein R is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 1000)
(3)
BiO X (OH) Y (NO 3) Z
(Wherein x is an integer or a prime number of 0.9 to 1.1, Y is a prime number of 0.6 to 0.8, and Z is a prime number of 0.2 to 0.4)
≪ Formula 4 >
Zr [HPO 4 ] 2 H 2 O
≪ Formula 5 >
Ti [HPO 4 ] 2 H 2 O
(6)
Zr 1-x Tix [HPO 4 ] 2 H 2 O
(Where x is a prime number of 0.25 to 0.75)
≪ Formula 7 >
Al 2 O 3 .3SiO 2
delete The method according to claim 1,
Wherein the EVA sheet for the solar cell encapsulant comprises one selected from a crosslinking agent and a crosslinking aid.
The method of claim 3,
The crosslinking agent is at least one selected from the group consisting of peroxyketals having a half-life of 1 hour at 110 to 120 ° C, peroxycarbonates having a half-life of 1 hour at 90 to 130 ° C, and dialkyl peroxides having a half- EVA sheets for solar cell bags.
5. The method of claim 4,
The peroxyketal may be 1,1-di (tert-amylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane or 1,1- -Butylperoxy) cyclohexane. ≪ / RTI >
5. The method of claim 4,
The peroxycarbonate may be 2,5-dimethyl-2,5-di- (2-ethylhexanonylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy- (2-ethylhexyl) monoperoxycarbonate, tert-butyl isopropyl monoperoxycarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert- -Ethylhexyl) monoperoxycarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate or tert-butylperoxybenzoate Features EVA sheet for solar cell bag material.
5. The method of claim 4,
The dialkyl peroxide is selected from the group consisting of dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane,?,? ' -tert-amyl peroxide, di-tert-butyl peroxide or 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3.
The method of claim 3,
Wherein the crosslinking agent is contained in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the total composition.
The method of claim 3,
The crosslinking aid may be selected from the group consisting of polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate and diallyl maleate, ethylene glycol diacrylate, ethylene glycol dimethacrylate and trimethyl And propane trimethacrylate in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the total composition of the EVA sheet for a solar cell encapsulant.
KR1020160178353A 2016-12-23 2016-12-23 Solar cell encapsulant EVA sheet KR101860651B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200061840A (en) 2018-11-26 2020-06-03 한국에너지기술연구원 Encapsulant and solar cell module for prevent pid, manufacturing method for the same
KR20200103609A (en) 2020-08-26 2020-09-02 한국에너지기술연구원 Encapsulant and solar cell module for prevent pid, manufacturing method for the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038624A (en) * 2015-08-05 2015-11-11 乐凯胶片股份有限公司 Photovoltaic EVA packaging adhesive film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038624A (en) * 2015-08-05 2015-11-11 乐凯胶片股份有限公司 Photovoltaic EVA packaging adhesive film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200061840A (en) 2018-11-26 2020-06-03 한국에너지기술연구원 Encapsulant and solar cell module for prevent pid, manufacturing method for the same
KR20200103609A (en) 2020-08-26 2020-09-02 한국에너지기술연구원 Encapsulant and solar cell module for prevent pid, manufacturing method for the same

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