TWI508315B - 具有對變色低敏感度之反射黏著膜的光伏打電池模組 - Google Patents
具有對變色低敏感度之反射黏著膜的光伏打電池模組 Download PDFInfo
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- TWI508315B TWI508315B TW100117670A TW100117670A TWI508315B TW I508315 B TWI508315 B TW I508315B TW 100117670 A TW100117670 A TW 100117670A TW 100117670 A TW100117670 A TW 100117670A TW I508315 B TWI508315 B TW I508315B
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- cell module
- photovoltaic cell
- film
- adhesive film
- pigment
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- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
- B32B17/10623—Whitening agents reflecting visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- 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
-
- 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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
-
- 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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/52—PV systems with concentrators
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Photovoltaic Devices (AREA)
Description
本發明是有關於使用具有對變色低敏感度之反射黏著膜之光伏打電池模組之產品。
光伏打電池模組常包含配置在一玻璃平板與一背蓋(back covering)之間的一感光層。尤其當背蓋亦由玻璃所構成時,這些元件係經由一個或多個由包含一軟化劑之聚乙烯醇縮丁醛(PVB)所製成之中間層膜而黏著在一起。
吾人亦知道少量之太陽光在不激發這些感光層的情況下通過它們。為了改善量子產率,尤其配置在感光層後方之黏著膜可包含例如二氧化鈦、二氧化鋯或金屬顏料之反射材料。二氧化鈦之使用作為一位在感光層後方之PVB薄膜中的反射顏料,係譬如從DE 4337694、WO 2009/071703、US 2007/0235077或US 5,059,254得知。
二氧化鈦係廣泛被使用作為一譬如在乳膠漆中之白色顏料,或用以將PVC異型材(profile)塗上顏色。不幸的是,在阿納斯塔斯修改(anastas modification)中,而如同達到一金紅石(rutile)修改中之較輕程度,二氧化鈦催化UV輻射中之一聚合物基(polymer matrix)之崩潰,所以商業上可得到的二氧化鈦顏料通常備有例如氧化矽、氧化鋁或二氧化鋯之惰性無機材料之一塗佈層。這些氧化物具有較低的折射率,從而亦具有實質上比二氧化鈦本身更低的散射力。當惰性塗佈層之比率增加時,各個顏料中之二氧化鈦之數量且同時顏料之散射效果也會被減少。為了保留一高度反射效果且同時尤其對光電流有高附加貢獻,具有最高可能的散射特性之二氧化鈦顏料(亦即尤其高的TiO2
含量)係用於光伏打電池應用。
然而,吾人觀察到在當其被壓緊在一PVB薄膜中時之電阻測試期間,具有一高TiO2
含量之金紅石型式之二氧化鈦在暴露至UV輻射時轉成藍色,且這大幅地減少薄膜之反射率。在疊層之邊緣區域中,效果係相當不顯著,且只有部分可逆,換言之於此之大氣中的氧氣係能擴散。在不對理論之優點加以推測的情況下,吾人認為所觀察到的效果係關於電子之中間狀態(intermediary state),其只可在缺乏氧之下依此方式而得以穩定。當大氣中的氧氣能夠沒有障礙的經由一未被玻璃覆蓋之黏著膜之表面穿過一光伏打電池模組時,這些效果並未依此方式產生。由於隨著在一PV模組暴露至太陽輻射期間之長期間之變色,在一光伏打電池模組中之一以二氧化鈦填滿之薄膜從而失去其大量的反射率。因此,模組之某些改善的初始性能亦隨著時間而失去。
因此,本發明之任務係用以提供包含用於光伏打電池模組之二氧化鈦之中間層膜,這些光伏打電池模組較不易於變色,從而顯現一反射率之較不重大的損失。
令人驚訝的是,吾人發現當包含較小量之TiO2
之二氧化鈦顏料係使用於一中間層膜時,雖然所達到的散射效應/反射率略微較低,但大幅地減少了反射率由於隨著時間變色之損失。一依此方式被裝備之薄膜具有一較長的服務壽命,並使得光伏打電池模組在它們的操作壽命之過程中更有效。
因此,本發明之目的係為由一疊層所製成之光伏打電池模組,此疊層係由下述元件所組成:
a)一透明前蓋;
b)一個或多個光敏半導體層;
c)至少一黏著膜;以及
d)一後蓋;
其中,至少一黏著膜係被裝備成反射的,並包含具有一50至94個重量百分比(相對於所使用的顏料)之TIO2
含量之二氧化鈦顏料。二氧化鈦顏料最好是包含金紅石修改中之TIO2
。
為擴散反射而裝備之黏著膜導致少量之通過光敏半導體層之光被反射回至其之上,藉以增加模組之效率。選擇的二氧化鈦顏料之使用抑制變色,且增加的效率係為模組之壽命而保留。舉例而言,WO 2009/071703揭露具有一94.5%之TiO2
分餾之二氧化鈦顏料之使用。令人驚訝的是,吾人發現包含較少量之TiO2
之顏料在暴露至太陽輻射之後具有較大的反射率。因為具有一較大分餾之TiO2
之原始反射率係大於具有較小的TiO2
分餾之顏料之反射率(其係如預期的),這是更令人驚訝。
依據下述所說明之測試方法,依據本發明所使用的薄膜在被暴露至UV輻射持續1000小時之前與之後兩者,顯露出於至少85%,最好是至少90%,且尤其至少95%之1100 nm下之反射率之保留。
依據本發明所使用的薄膜最好是包含二氧化鈦顏料,其係利用來自氧化鋅、氧化矽、氧化鋁與二氧化鋯之群組之一個或多個化合物來塗佈。所使用之塗佈層材料最好是氧化矽與氧化鋁之一混合物。
依據本發明所使用的二氧化鈦顏料具有一最好是10-80 nm,更好是15-60 nm,尤其最好是20-40 nm之平均粒子尺寸。
因此,依據本發明用於薄膜之二氧化鈦顏料之無機部分包含一最大94個重量百分比的TiO2
。依據本發明所使用之顏料最好是包含一最大93個重量百分比,尤其最好是一最大92個重量百分比的TiO2
,甚至最好是一最大91個重量百分比的TiO2
。然而,在二氧化鈦顏料中之TiO2
含量應該是50% TiO2
以上,最好是70% TiO2
以上,尤其最好是80% TiO2
以上,而甚至最好是85%以上,否則薄膜之反射率將不充分。
此外,為了促進薄膜基質中之均勻的含有物,二氧化鈦顏料可任意地利用有機化合物而受到表面處理。這種化合物之例子係為有機磷、有機硫酸鹽、聚矽氧烷或例如聚二甲基矽氧烷(PDMS)之矽酮化合物。表面處理最好是由一例如PDMS之矽酮化合物所組成。多官能醇(舉例而言TMP)係較不適當,因為它們可能增強藍色變色。
除構成其餘的二氧化鈦顏料之TiO2
之外的部分,係由上述所引證的無機及/或有機化合物所組成。
依據本發明所使用之反射黏著膜最好是一單層膜。然而,如果反射黏著膜包含至少一反射層(換言之含顏料層)(局部薄膜),以及至少一非反射層,換言之無顏料層(局部薄膜),其可能是有利的。因此,譬如一個或兩個外局部層可確保黏著效果,而包含反射顏料並配置於這兩個之間的反射局部薄膜會執行反射輻射之功能。
具有多重局部層之薄膜可能藉由接合預製的局部層或藉由在一單一製程周期中之局部層之共壓出成型(coextrusion)而產生。
反射黏著膜中之二氧化鈦顏料之分餾最好是至少5個重量百分比,尤其最好是至少8個重量百分比或至少10個重量百分比,且更好是至少12個重量百分比。30個重量百分比之上限應在每個情況下被觀察。如果黏著膜係由無顏料與含顏料局部層所構成,則這個數值指的是薄膜之全部,其意味著依據厚度分佈,較高濃度之TiO2
可能使用於含顏料局部層中。
如果反射中間層係由至少一無顏料與至少一含顏料局部層所組成,則這些局部層每個可具有一不同的或相同的組成物及/或包含聚合物材料。
用於反射黏著與局部層之材料可能是用以製造複合夾疊玻璃嵌板之已知材料,例如PVC、Geniomer(聚二甲基矽氧烷/尿素共聚物)、矽酮、聚氨酯、乙烯/醋酸乙烯酯(EVA)、環氧灌注樹脂、離子聚合物、聚鏈烯烴,或特別是包含一軟化劑之聚乙烯醇縮乙醛或包含一軟化劑之聚乙烯醇縮丁醛。
這些包含具有一軟化劑之聚乙烯醇縮乙醛之薄膜最好是包含非交聯的聚乙烯醇縮丁醛(PVB),其係藉由具有丁醛之聚乙烯醇之縮醛反應(acetalisation)而獲得。
交聯的聚乙烯醇縮乙醛、尤其是交聯的聚乙烯醇縮丁醛(PVB)之使用亦是可能的。適當的交聯的聚乙烯醇縮乙醛係譬如在EP 1527107 B1與WO 2004/063231 A1(包含羧基群組之聚乙烯醇縮乙醛之熱自交聯)、EP 1606325 A1(與聚醛基高分子(polyaldehyde)交聯的聚乙烯醇縮乙醛)以及WO 03/020776 A1(與乙醛酸交聯的聚乙烯醇縮乙醛)中被說明。這些專利申請之揭露內容之整體係併入作參考。
亦可能用以利用其他或額外具有5-10碳原子之醛(舉例而言,例如戊醛)來執行縮醛反應。
在不超過本發明之範疇的情況下,來自水解醋酸乙烯酯/乙烯共聚體之三元共聚物亦可被使用作為聚乙烯醇。這些化合物通常是98%以上水解的,並包含1至10個乙烯式重量單元(舉例而言,屬於由Kuraray Europe GmbH所製造之型式"Exceval")。
除乙縮醛單元以外,聚乙烯醇縮乙醛亦包含由醋酸乙烯酯與乙烯醇所產生的單元。包含依據本發明所使用之軟化劑之聚乙烯醇縮乙醛最好是包含一少於20個重量百分比,少於18個重量百分比,或尤其少於16個重量百分比之聚乙烯醇分餾。聚乙烯醇之分餾不應少於12個重量百分比。聚乙烯醇縮乙醛中之聚乙烯醋酸鹽之分餾最好是少於5個重量百分比,尤其少於3個重量百分比,且尤其少於2個重量百分比。縮醛反應之程度可能由聚乙烯醇分餾與剩下的醋酸鹽含量而算術地被計算出。
依據本發明所使用之反射薄膜最好是在環境濕度85% RH中,於23℃下,具有一至少1E+11歐姆*公分(ohm*cm),更好是至少5E+11 ohm*cm,最好是1E+12 ohm*cm,最好是5E+12 ohm*cm,最好是1E+13,最好是5E+13 ohm*cm,最好是1E+14 ohm*cm之電阻率。
依據本發明所使用之薄膜,尤其那些基於含軟化劑之聚乙烯醇縮乙醛具有40個重量百分比、35個重量百分比、32個重量百分比、30個重量百分比、28個重量百分比、26個重量百分比、24個重量百分比、22個重量百分比、20個重量百分比、18個重量百分比、16個重量百分比之最大的軟化劑含量,且軟化劑含量不應少於15個重量百分比,以便保留薄膜的加工性(相對於每個情況下之總薄膜配方)。薄膜或光伏打電池模組可包含一個或多個軟化劑。
依據本發明所使用之原則上適合於聚乙烯醇縮乙醛式薄膜之軟化劑係為來自下述群組之一個或多個化合物:-多價脂肪或芳香酸之酯,譬如己二酸二烷基(dialkyl adipates),例如己二酸二正己酯(dihexyl adipate)、己二酸二辛酯(dioctyladipate)、己二酸己基環己基(hexylcyclohexyl adipate)、庚-和壬基己二酸之混合物、己二酸二異壬(diisononyl adipate)、己二酸庚基壬基(heptylnonyl adipate),以及具有脂環族醇酯或具有包含醚化合物之醇酯之己二酸之酯,癸二酸二烷基酯(dialkyl sebacate),例如癸二酸二丁酯與具有脂環族醇酯或具有包含醚化合物之醇酯之癸二酸之酯,鄰苯二甲酸之酯,例如鄰苯二甲酸丁芐酯(butylbenzyl phthalate)或鄰苯二甲酸二(2-丁氧基乙基)酯(bis-2-butoxyethyl phthalate)-多價脂肪或芳香醇或具有一個或多個不分支或分支脂肪族或芳香族取代基之低聚醚甘醇之酯,舉例而言,具有線性或分支脂肪族或脂環族羧酸之二、三或四甘醇之酯;下述可作為最終群組之例子:二乙烯基乙二醇-雙-(2-乙基己酸)(diethylene glycol-bis-(2-ethylhexanoate))、三乙烯基乙二醇-雙-(2-乙基己酸)(triethylene glycol-bis-(2-ethylhexanoate))、三乙烯基乙二醇-雙-(2-乙基丁酸酯)(triethylene glycol-bis-(2-ethylbutanoate)、四乙烯基乙二醇-雙-n-庚酸(tetraethylene glycol-bis-n-heptanoate)、三乙烯基乙二醇-雙-n-庚酸(triethylene glycol-bis-n-heptanoate)、三乙烯基乙二醇-雙-n-己酸(triethylene glycol-bis-n-hexanoate)、四乙烯基乙二醇二甲醚(tetraethylene glycol dimethylether)及/或二丙二醇苯甲酸(dipropylene glycol benzoate)-具有脂肪族或芳香醇酯之磷酸鹽,例如磷酸三(2-乙基己基)酯(tris(2-ethylhexyl) phosphate(TOF))、磷酸三乙酯(triethyl phosphate)、磷酸二苯辛酯(diphenyl-2-ethylhexyl phosphate)及/或磷酸三甲苯酯(tricresyl phosphate)-檸檬酸之酯,伯恩斯坦酸(Bernstein acid)及/或反丁烯二酸(fumaric acid)選自於下述群組之一個或多個化合物,對於基於依據本發明所使用之聚乙烯醇縮乙醛之薄膜而言係為高度適當的軟化劑:癸二酸二辛酯(di-2-ethylhexyl sebacate(DOS))、己二酸二辛酯(di-2-ethylhexyl adipate(DOA))、己二酸二己酯(dihexyl adipate(DHA))、癸二酸二丁酯(dibutyl sebacate(DBS))、三乙烯基乙二醇-雙-n-庚酸(triethylene glycol-bis-n-heptanoate(3G7))、四乙烯基乙二醇-雙-n-庚酸(tetraethylene glycol-bis-n-heptanoate(4G7))、三乙烯基乙二醇-雙-2-乙基己酸(triethylene glycol-bis-2-ethylhexanoate(3GO或3G8))、四乙烯基乙二醇-雙-n-2-乙基己酸(tetraethylene glycol-bis-n-2-ethylhexanoate(4GO或4G8))、己二酸雙(2-丁氧乙基)酯(di-2-butoxyethyl adipate(DBEA))、己二酸雙(2-丁氧基乙氧基)乙酯(di-2-butoxyethoxy ethyl adipate(DBEEA))、癸二酸雙(2-丁氧基乙基)酯(di-2-butoxy ethyl sebacate(DBES))、鄰苯二甲酸二(2-乙基己基)酯(di-2-ethylhexyl phthalate(DOP))、鄰苯二甲酸二異壬酯(di-isononyl phthalate(DINP))、三乙烯基乙二醇-雙-異壬酸酯(triethylene glycol-bis-isononanoate)、三乙烯基乙二醇-雙-2-己酸丙酯(triethylene glycol-bis-2-propyl hexanoate)、磷酸三(2-乙基己基)酯(tris(2-ethylhexyl)phosphate(TOF))、1,2環己二異壬酯酸(1,2-cyclohexane dicarboxylic acid diisononyl ester(DINCH))、己二酸二異壬(diisononyl adipate(DINA))與二丙二醇苯甲酸(dipropylene glycol benzoate)。
對依據本發明所使用之聚乙烯醇縮乙醛式薄膜而言,特別適當的軟化劑係為物質,其以配方100 x O/(C+H)所表示的極性係小於/等於9.4,其中O、C與H代表各個分子中之氧、碳與氫原子之數目。下表列出依據本發明可用的軟化劑,與依據配方100 x O/(C+H)之它們的極性值一起列出。
舉例而言,玻璃上之聚乙烯醇縮乙醛薄膜之黏著強度,通常係藉由添加例如揭露於WO 03/033583 A1中之有機酸之鹼及/或鹼性土鹽之黏著調節劑而調整。醋酸鉀及/或醋酸鎂已證明是特別適合的。因為生產製程之結果,聚乙烯醇縮乙醛常包含無機酸之鹼及/或鹼性土鹽,譬如氯化鈉。
因為鹼金屬鹽對電阻率亦具有一影響,所以使用包含軟化劑(包含少於100 ppm,最好是少於50 ppm且特別是少於30 ppm鹼金屬離子)之聚乙烯醇縮乙醛式薄膜是方便的。這可能利用聚乙烯醇縮乙醛之適當的清洗製程並藉由使用選自於鹼土金屬、鋅與鋁鹽之群組之多價金屬鹽作為鹼性安定劑而達成。鎂鹽,尤其是醋酸鎂、丙酸鎂、丁酸鎂、己酸鎂、辛酸鎂與硬脂酸鎂對於此是較佳的。依據本發明所使用之反射薄膜具有一鹼滴定量(alkali titer),最好是大於0,尤其最好是大於5,特別好是大於10或大於15。不應超過100之鹼滴定量,否則薄膜可能呈現一黃變色。
可能取決於薄膜之含水量之離子遷移率及與此相關的電阻率,亦可藉由熱成性(pyrogenic)二氧化矽之附加而變化。含軟化劑之聚乙烯醇縮乙醛式薄膜最好是包含0.001至15個重量百分比,尤其是2至5個重量百分比熱成性SiO2
。
舉例而言,聚乙烯醇縮乙醛式薄膜之生產與組成物,原則上係說明於EP 185 863 B1、EP 1 118 258 B1、WO 02/102591 A1、EP 1 118 258 B1或EP 387 148 B1中。
光伏打電池模組係藉由使薄膜熔解而被堆疊,用以獲得一具有沒有氣泡與條紋之薄膜之半導體層之含有物。
黏著膜之整體厚度通常是0.30、0.38、0.45、0.51、0.76、1.14 mm。
在疊層製程期間,依據本發明所使用之薄膜填滿存在於光敏半導體層與它們的電性連接中之孔穴。
透明前蓋一般係由玻璃或PMMA所製成。依據本發明之光伏打電池模組之背蓋可能由玻璃、塑膠或金屬,或其之複合物所製成,其中至少一支撐可能是透明性。亦可能以夾疊玻璃平板(換言之作為一至少兩個玻璃嵌板與至少一PVB薄膜之疊層)之型式或以具有一充氣間隙之絕緣鑲玻璃(insulating glazing)之型式建構一個或兩個遮蓋物。當然亦可能結合這些方法。
使用於模組之光敏半導體層並不需要具有任何特殊特性。單晶矽、多晶矽或非晶矽系統可能被使用。
當依據本發明之薄膜太陽能模組被製造時,光敏半導體層通常被直接塗敷至透明遮蓋物,並與具有依據本發明之至少一黏著膜之後蓋接合。
當結晶矽或支援的太陽能模組被製造時,太陽能模組必須被納入黏著膜中,換言之,依據本發明,光敏半導體層b)係經由至少一非反射黏著膜與透明前蓋a)接合,並經由至少一黏著膜與後蓋d)接合。除了反射顏料以外,這些膜最好是具有與反射黏著膜相同的組成物。
因此所獲得之疊層本體可能藉由熟習本項技藝者所熟悉的用以在有與無一複合前驅物之先前生產的情況下疊層之任何一個方法而疊層。
「壓力鍋製程」係在大約10至15巴(bar)之加壓之下與於130至145℃之溫度持續大概2小時而被執行。如譬如說明於EP 1 235 683 B1中之真空袋或真空環方法係於大約200毫巴(mbar)與130至145℃下被實施。
依據本發明之光伏打電池模組最好是藉由真空層壓機的協助而被製造。真空層壓機包含一容室,其可被加熱並排出,於其中複合玻璃嵌板可在10至60分鐘之內被堆疊。從0.01至300毫巴之局部真空與從100至200℃,尤其130至160℃之溫度實際上已經證明是有效的。
或者,一如上所述所製造之疊層本體可能於60至150℃之溫度下被壓縮在至少一滾輪對之間以形成依據本發明之模組。此種適合複合玻璃嵌板之生產之機器係已知的,且在具有兩個按壓裝置(pressing plant)之系統中的第一按壓裝置之前及/或之後正常設有至少一加熱隧道。
依據本發明之光伏打電池模組可能使用作為外觀元件(facade element)、頂板(roof panel)、溫室遮蓋物、隔音牆、陽台或欄杆元件,或作為窗戶表面之組件。
薄膜之電阻率係在薄膜已於此環境被空調持續至少24小時之後,以界定的溫度與環境濕度(23℃與85% RH)而依據DIN IEC 60093被測量。一種由Fetronic GmbH所製造之型號302 132平板電極以及一種由Amprobe所製造之ISO-Digi 5kV電阻計係用以執行測量。測試電壓係為2.5 kV,在施加測試電壓直到記錄到測量值為止之後的等待時間係為60秒。依據DIN EN ISO 4287,為了測量之目的,為了確保在測量電極與薄膜之平板之間的充分接觸,其表面粗糙度Rz
不應大於10μm,換言之PVB薄膜之原始表面可能在採取電阻測量之前藉由熱重鑄(thermal recoining)而必須是平坦的。
聚乙烯醇縮乙醛之聚乙烯醇以及聚乙烯醇醋酸鹽含量係依據ASTM D 1396-92而決定。薄膜之水或水分含量係藉由使用卡爾費雪(Karl Fischer)方法而決定。
3至4克的含軟化劑之聚乙烯醇縮乙醛薄膜係以一磁力攪拌器而整夜被溶解在100 ml之一乙醇/THF(80:20)之混合物中。10 ml之一稀釋鹽酸(c=0.01克分子/公升)係加至此,而混合物係接著利用一種四丁基氫氧化銨(TBAH)在2丙醇(c=0.01克分子/公升)之溶液被電位滴定,以對比一利用一滴定儀(titroprocessor)之對照樣品。鹼滴定量係計算如下:鹼滴定量=ml HCl每100 g之樣品=(TBAH對照樣品之消耗-TBAH樣品x 100除以樣品之重量(g))。
具有表中顯示之二氧化鈦顏料之組成物之含軟化劑之聚乙烯醇縮丁醛薄膜,係關於它們用以作為光伏打電池模組中之反射黏著膜的適當性而受到調查。薄膜由具有以重量百分比表示的聚乙烯醇(PVOH)含量以及一大約1個重量百分比之聚乙烯醋酸鹽含量之軟化的聚乙烯醇縮丁醛(PVB)所組成。
各種TiO2
型式之輻射電阻係針對組成物之玻璃/玻璃夾層而作比較:- 2 mm Optiwhite(由Pilkington所生產之低鐵玻璃)- 0.76 mm PVB薄膜,以各個二氧化鈦顏料之重量計包含12.5個百分比- 2 mm Optiwhite薄膜係在包含在疊層中之前,在23℃/23% RH之氣候下被空調持續24小時,玻璃嵌板係在一玻璃洗滌機中以於50℃下之溫去礦物質水被清洗。然後,在一種一般用以製造複合玻璃之滾動/蒸壓養護製程(autoclaving)中與於一140℃之最大溫度下生產疊層。
疊層樣品係在一種「Q-SUN氙測試容室模型Xe-3-HBS」中被照射持續1000小時。於340 nm下之輻射強度係為0.55 W/m2
,跟80℃之黑色瓦溫,45℃與20%相對濕度之空氣溫度。反射係在輻射之前以及在樣品從輻射室被移除之後的24小時,依據EN 410而基於一由Perkin Elmer所製造之Lambda 950 UV/VIS/NIR光譜儀被測量。來自光譜之各個反射率數值係於1100 nm之波長下被讀取。
比較例1-3顯示未依據本發明之關於包含一TiO2
分餾之二氧化鈦顏料之反射率數值在輻射之後係比依據本發明之顏料(例1-4)大幅變差。在例2與比較例2之間的比較尤其顯示出依據本發明之薄膜儘管它們有較低的TiO2
分餾仍具有較高的反射率,黏著膜之組成物在其他方面是相同的。
圖1、2與3以依據例1、3與比較例3之疊層樣品之%顯示反射率隨著一散射光之波長之函數。上曲線顯示輻射之前的反射率,下曲線顯示輻射之後的反射率。
下表之數值與圖顯示無論顏料型式(依據製造商之說明書)之一相當低的散射能力為何,依據本發明所建構之中間薄膜顯示在輻射之後有較少變色與較大反射率。這種薄膜因此尤其十分適合用以製造光伏打電池模組。
表中之所有資訊係以重量百分比相對於薄膜混合物來給予,換言之,是相對於總數(PVB、軟化劑與TiO2
)來給予。PVB中之PVOH含量係與PVB相關聯,TiO2
含量係與所使用之二氧化鈦顏料相關聯。Mg(醋酸鹽)2 x 4 H2
O係被添加以作為一抗黏著劑。
所使用之二氧化鈦係從Kronos公司所標示之產品名稱獲得。
圖1、2與3以依據例1、3與比較例3之疊層樣品之%顯示反射率隨著一散射光之波長之函數。上曲線顯示輻射之前的反射率,下曲線顯示輻射之後的反射率。
Claims (11)
- 一種光伏打電池模組,由下述元件所組成之一疊層所製成:a)一透明前蓋;b)一個或多個光敏半導體層;c)至少一個黏著膜;以及d)一後蓋;其特徵在於至少一個黏著膜係一反射黏著層,並包含具有50至94個重量百分比之TiO2 含量之一二氧化鈦顏料。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該二氧化鈦顏料係利用來自氧化鋅、氧化矽、氧化鋁及/或二氧化鋯之該群組之一個或多個化合物來塗佈。
- 如申請專利範圍第2項所述之光伏打電池模組,其中該二氧化鈦顏料係利用氧化矽與氧化鋁之一混合物來塗佈。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該些二氧化鈦顏料係利用一矽酮化合物、一聚矽氧烷、一有機硫酸鹽化合物及/或一有機磷化合物而受到表面處理。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜係由至少一個無顏料與至少一個含顏料局部薄膜所組成。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜係由至少一個無顏料與至少一個含顏料局部薄膜所組成,且這些局部層包含相同的聚合物材料。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜包含至少一個聚乙烯醇縮乙醛,其包含軟化劑。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜具有大於0之一鹼滴定量。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜包含一聚乙烯醇縮乙醛,其具有軟化劑並包含小於20個重量百分比之一聚乙烯醇含量。
- 如申請專利範圍第1項所述之光伏打電池模組,其中該反射黏著膜包含選自於下述該群組之至少一個軟化劑:癸二酸二辛酯(di-2-ethylhexyl sebacate(DOS))、1,2環己二異壬酯酸(1,2-cyclohexane dicarboxylic acid diisononyl ester(DINCH))、己二酸二異壬(diisononyl adipate(DINA))、己二酸二辛酯(di-2-ethylhexyl adipate(DOA))、鄰苯二甲酸二(2-乙基己基)(di-2-ethylhexyl phthalate(DOP))、己二酸二正己酯(dihexyl adipat(DHA))、癸二酸二丁酯(DBS)、三乙烯基乙二醇-雙-2-己酸丙酯(triethylene glycol-bis-2-propyl hexanoate)、三乙烯基乙二醇-雙-i-壬酸酯(triethylene glycol-bis-i-nonanoate)、癸二酸雙(2-丁氧基乙基)酯(di-2-butoxyethyl sebacate(DBES))以及三乙烯基乙二醇-雙-2-乙基己酸(triethylene glycol-bis-2-ethyl hexanoate(3G8))。
- 如申請專利範圍第1至10項中任一項所述之光伏打電池模組,其中該反射黏著膜在85% RH之環 境濕度中與於23℃下,具有一至少1E+11ohm*cm之電阻率。
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EP10165622A EP2395558A1 (de) | 2010-06-11 | 2010-06-11 | Photovoltaikmodule mit reflektierenden Klebefolien geringer Verfärbungsneigung |
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TWI508315B true TWI508315B (zh) | 2015-11-11 |
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US (1) | US20110303279A1 (zh) |
EP (2) | EP2395558A1 (zh) |
CN (1) | CN102280506B (zh) |
TW (1) | TWI508315B (zh) |
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JP2014103264A (ja) * | 2012-11-20 | 2014-06-05 | Toshiba Corp | 光電変換素子および太陽電池 |
EP2746044A1 (de) * | 2012-12-20 | 2014-06-25 | Kuraray Europe GmbH | Photovoltaikmodule mit effizienzsteigernden Klebefolien |
JP2014179462A (ja) * | 2013-03-14 | 2014-09-25 | C I Kasei Co Ltd | 太陽電池モジュール用裏側封止材及び太陽電池モジュール |
JP6217328B2 (ja) * | 2013-11-11 | 2017-10-25 | 信越化学工業株式会社 | 太陽電池封止用紫外線遮蔽性シリコーン接着剤シート並びにそれを用いた太陽電池モジュール |
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2010
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2011
- 2011-05-20 TW TW100117670A patent/TWI508315B/zh not_active IP Right Cessation
- 2011-06-08 US US13/155,458 patent/US20110303279A1/en not_active Abandoned
- 2011-06-10 EP EP11169424A patent/EP2395561B1/de not_active Not-in-force
- 2011-06-10 CN CN201110155535.2A patent/CN102280506B/zh not_active Expired - Fee Related
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TW200833415A (en) * | 2006-12-08 | 2008-08-16 | Degussa | Dispersion containing titanium dioxide |
EP1938964A1 (en) * | 2006-12-29 | 2008-07-02 | E.I. Du Pont De Nemours And Company | Intrusion resistant safety glazings and solar cell modules |
WO2009071703A2 (de) * | 2007-12-07 | 2009-06-11 | Kuraray Europe Gmbh | Photovoltaikmodule mit reflektierenden klebefolien |
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CN102280506B (zh) | 2017-04-12 |
EP2395558A1 (de) | 2011-12-14 |
US20110303279A1 (en) | 2011-12-15 |
TW201210051A (en) | 2012-03-01 |
CN102280506A (zh) | 2011-12-14 |
EP2395561A1 (de) | 2011-12-14 |
EP2395561B1 (de) | 2013-03-06 |
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