TWI459569B - Method for recycling photovoltaic cell modules - Google Patents
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- TWI459569B TWI459569B TW100129158A TW100129158A TWI459569B TW I459569 B TWI459569 B TW I459569B TW 100129158 A TW100129158 A TW 100129158A TW 100129158 A TW100129158 A TW 100129158A TW I459569 B TWI459569 B TW I459569B
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本發明係有關一種太陽能電池模組之回收方法,特別是一種利用分段式加熱的太陽能電池模組之回收方法。The invention relates to a recycling method of a solar cell module, in particular to a recycling method of a solar cell module using segment heating.
隨著太陽能的裝置量不斷提高,未來勢必產生大量的廢棄太陽能電池模組,因此太陽能電池模組的分解與回收方法將是未來非常重要的一個技術。As the amount of solar energy equipment continues to increase, a large number of discarded solar cell modules will inevitably be generated in the future. Therefore, the decomposition and recycling method of solar cell modules will be a very important technology in the future.
以傳統矽晶太陽能模組結構為例,其構造組成包含多晶或單晶之太陽能電池片、串接各電池片之焊條(主成分為銅錫)、封裝固定太陽能電池片及焊條的封裝膜、背板、及正面的玻璃板,其中封裝膜和背板通常為塑膠材質,例如分別為乙烯醋酸乙烯酯(ethylene vinyl acetate,EVA)與聚氟乙烯(polyvinyl fluoride,PVF),而上述各成分所佔之重量%約為:玻璃65.8 wt%、塑膠材料10.4 wt%、太陽能電池片2.9 wt%、焊條1 wt%、鋁框17.5%、及接線盒2.4 wt%。為了進行太陽能電池模組各材料的回收,必須將太陽能模組分解,其中鋁框與接線盒可輕易的拆除回收,剩下的材料由於被例如EVA的塑膠材質穩固的包覆住,必須要使用特殊處理才能進一步分解。Taking a traditional twin crystal solar module structure as an example, the structural composition comprises a polycrystalline or single crystal solar cell, a welding electrode serially connected to each cell (the main component is copper tin), a packaged fixed solar cell sheet and an electrode encapsulating film. a back sheet, and a front glass sheet, wherein the encapsulating film and the back sheet are usually made of a plastic material, such as ethylene vinyl acetate (EVA) and polyvinyl fluoride (PVF), respectively. The weight % is about 65.8 wt% of glass, 10.4 wt% of plastic material, 2.9 wt% of solar cell, 1 wt% of electrode, 17.5% of aluminum frame, and 2.4 wt% of junction box. In order to recover the materials of the solar cell module, the solar module must be decomposed. The aluminum frame and the junction box can be easily removed and recycled. The remaining materials must be used because they are firmly covered by the plastic material such as EVA. Special treatment can be further broken down.
EVA與PVF為熱固性塑膠材質,在加熱下並不會熔化,而是在到達一定溫度範圍時直接燃燒分解。因此在分解矽晶太陽能電池模組時所遭遇到的一個困難是如何有效地移除例如EVA及PVF等的塑膠材料。先前文獻(Solar Energy Materials & Solar Cells 67(2001)397-403)提到利用將太陽能電池模組浸泡於酸液或有機溶劑中來分解EVA,然而酸液或有機溶劑需要一段時間才能滲透進入太陽能電池模組,對於大面積模組來說,溶液必須要花費長達數十小時才能滲透到達模組中心處,因此上述酸液或有機溶劑浸泡法只能侷限於小面積模組。此外,使用有機溶劑對於環境也較容易造成污染。EVA and PVF are thermosetting plastic materials that do not melt under heating, but directly burn and decompose when they reach a certain temperature range. Therefore, one of the difficulties encountered in decomposing a twin solar cell module is how to effectively remove plastic materials such as EVA and PVF. The previous literature (Solar Energy Materials & Solar Cells 67 (2001) 397-403) mentions the use of solar cell modules immersed in acid or organic solvents to decompose EVA, but acid or organic solvents take some time to penetrate into solar energy. For battery modules, for large-area modules, the solution must take up to tens of hours to penetrate the center of the module. Therefore, the above acid or organic solvent immersion method can only be limited to small-area modules. In addition, the use of organic solvents is also more likely to cause pollution to the environment.
移除EVA與PVF的另一方法為加熱。美國專利US 6,063,995揭露在480℃~520℃的溫度下加熱矽晶太陽能電池模組以分離玻璃板與太陽能電池片,並且在加熱過程中通入惰性氣體以避免太陽能電池模組中塑膠的碳化及燃燒。然而EVA在高溫過程中會產生形變,造成太陽能電池片與玻璃板的破裂,因此幾乎不可能順利得到完整的太陽能電池片與玻璃板。此外在加熱製程中通入大量惰性氣體(例如氮氣)將造成排氣端出現大量灰份,而含有灰份的氣體造成分離上的困難。由前述的數據可知,在矽晶太陽能電池模組各組成中玻璃板佔了非常大的比例(65.8 wt%),因此玻璃板的回收也是矽晶太陽能模組回收的重點項目之一。如果可以在模組分解過程中維持玻璃板的完整性,就可以將回收的玻璃板直接再次使用在模組封裝上,這對於降低生產成本以及減少垃圾污染將有非常大的幫助。Another method of removing EVA from PVF is heating. US 6,063,995 discloses heating a twinned solar cell module at a temperature of 480 ° C to 520 ° C to separate the glass plate from the solar cell, and introducing an inert gas during the heating process to avoid carbonization of the plastic in the solar cell module. combustion. However, EVA will deform during the high temperature process, causing the solar cell and the glass plate to rupture, so it is almost impossible to obtain a complete solar cell and glass plate smoothly. In addition, the introduction of a large amount of inert gas (for example, nitrogen) in the heating process causes a large amount of ash to appear at the exhaust end, and the gas containing ash causes difficulty in separation. It can be seen from the above data that the glass plate accounts for a very large proportion (65.8 wt%) in the composition of the twin solar cell module, so the recovery of the glass plate is also one of the key projects for the recovery of the twin crystal solar module. If the integrity of the glass plate can be maintained during the module decomposition process, the recycled glass plate can be directly reused on the module package, which is very helpful for reducing production costs and reducing garbage pollution.
因此,亟需提出一種可解決上述問題的太陽能電池模組的回收方法。Therefore, there is a need to propose a recycling method for a solar cell module that can solve the above problems.
本發明係提供一種太陽能電池模組的回收方法,包括:(a)提供一太陽能電池模組,包括:一太陽能電池片;一對封裝膜夾設該太陽能電池片;一背板與一玻璃板夾設該對封裝膜;(b)於330-380℃的溫度下加熱該太陽能電池模組,以分離該對封裝膜及該背板;(c)於400-450℃的溫度下加熱該太陽能電池模組,以碳化該分離後之該對封裝膜及該背板;及(d)回收該玻璃板。The invention provides a method for recycling a solar cell module, comprising: (a) providing a solar cell module comprising: a solar cell sheet; a pair of encapsulating films sandwiching the solar cell sheet; a back sheet and a glass sheet Sandwiching the pair of package films; (b) heating the solar cell module at a temperature of 330-380 ° C to separate the pair of package films and the back plate; (c) heating the solar energy at a temperature of 400-450 ° C a battery module for carbonizing the separated pair of package films and the back sheet; and (d) recovering the glass sheet.
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉出較佳實施例,並配合所附圖式,作詳細說明如下:The above and other objects, features and advantages of the present invention will become more <RTIgt;
以下特舉出本發明之實施例,並配合所附圖式作詳細說明,而在圖式或說明中所使用的相同符號表示相同或類似的部分,且在圖式中,實施例之形狀或是厚度可擴大,並以簡化或是方便標示。再者,圖式中各元件之部分將以分別描述說明之,值得注意的是,圖式中未繪示或描述之元件,為所屬技術領域中具有通常知識者所知的形狀。此外,當某一層被描述為在另一層(或基底)上或上方時,其可代表該層與另一層(或基底)為直接接觸,或兩者之間另有其他層存在。另外,特定之實施例僅為揭示本發明使用之特定方式,其並非用以限定本發明。The embodiments of the present invention are described in detail below with reference to the drawings, and the same reference numerals are used in the drawings or the description of the same or similar parts, and in the drawings, the shapes of the embodiments or The thickness can be enlarged and simplified or conveniently marked. Further, portions of the various elements in the drawings will be described separately, and it is noted that elements not shown or described in the drawings are shapes known to those of ordinary skill in the art. Further, when a layer is described as being on or over another layer (or substrate), it can mean that the layer is in direct contact with another layer (or substrate) or otherwise. In addition, the specific embodiments are merely illustrative of specific ways of using the invention, and are not intended to limit the invention.
第1圖顯示根據於本發明實施例之太陽能電池模組回收流程示意圖。然而應能理解的是,第1圖所示之流程示意圖僅為範例而並非詳盡,且可在各步驟之中或者之間進行其他的步驟。第1圖從提供一太陽能電池模組的步驟10開始,接著進行步驟20,其中於330-380℃的溫度下加熱太陽能電池模組,以分離封裝膜及背板,再進行步驟30,其中於400-450℃的溫度下加熱太陽能電池模組,以碳化該分離後之封裝膜及背板。完成加熱後,可直接或間接地回收分離出的玻璃板(步驟40)、焊條(步驟50)、及太陽能晶片(步驟60)。舉例來說,分離出的玻璃板若為完整的,可直接重複使用。另一方面,可純化分離出的焊條,以回收焊條所含之金屬。再者,可以酸及/或鹼蝕刻溶液清洗太陽能電池片,以得到太陽能晶片。FIG. 1 is a schematic view showing a recycling process of a solar cell module according to an embodiment of the present invention. However, it should be understood that the schematic flow diagram shown in FIG. 1 is merely exemplary and not exhaustive, and other steps may be performed among or among the steps. Figure 1 begins with the step 10 of providing a solar cell module, and then proceeds to step 20, in which the solar cell module is heated at a temperature of 330-380 ° C to separate the encapsulation film and the back plate, and then step 30 is performed. The solar cell module is heated at a temperature of 400-450 ° C to carbonize the separated encapsulation film and back sheet. Upon completion of the heating, the separated glass sheet (step 40), the electrode (step 50), and the solar wafer (step 60) may be recovered directly or indirectly. For example, if the separated glass plate is intact, it can be reused directly. On the other hand, the separated electrode can be purified to recover the metal contained in the electrode. Further, the solar cell sheet may be cleaned with an acid and/or alkali etching solution to obtain a solar wafer.
在本發明之實施例中,首先提供一如第2圖所示之太陽能電池模組100。應可理解的是,第2圖中的太陽能電池模組僅為舉例說明,本發明的回收方法並非以此為限。太陽能電池模組可為各類不同的太陽能電池模組,例如P型或N型的太陽能電池、傳統太陽能電池結構、背面接觸式電池結構(metal wrap through,MWT)、異質接面電池結構(heterojunction with intrinsic thin layer,HIT)、選擇性射極電池結構(selective emitter)等。在較佳實施例中,太陽能電池模組100為一單晶矽或多晶矽太陽能電池模組。In an embodiment of the invention, a solar cell module 100 as shown in Fig. 2 is first provided. It should be understood that the solar cell module in FIG. 2 is merely illustrative, and the recycling method of the present invention is not limited thereto. The solar cell module can be a variety of different solar cell modules, such as P-type or N-type solar cells, conventional solar cell structures, metal wrap through (MWT), heterojunction cell structures (heterojunction) With intrinsic thin layer, HIT), selective emitter cell structure (selective emitter) and the like. In a preferred embodiment, the solar cell module 100 is a single crystal germanium or polycrystalline germanium solar cell module.
參見第2圖,本實施例的太陽能電池模組100可包括太陽能電池片1、串連太陽能電池片1的焊條2、一對夾設太陽能電池片1與焊條2的封裝膜3、設置於太陽能電池片正面上的玻璃板5、及設置於太陽能電池片1反面上的背板4,其中玻璃板5及背板4夾設該對封裝膜3。焊條2可為銅錫合金,但不限定於此且可為其他合適金屬或合金。封裝膜3完全包覆太陽能電池片1與焊條2的周圍。本實施例之封裝膜3的材料通常為乙烯醋酸乙烯酯(ethylene vinyl acetate,EVA),而背板4的材料通常為聚氟乙烯(polyvinyl fluoride,PVF),例如DuPontTM Tedlar。在一些實施例中,背板4可為一複合層,其中包括兩層PVF層4a,並且在兩層中間夾有一聚酯(polyester)層。Referring to FIG. 2 , the solar cell module 100 of the present embodiment may include a solar cell sheet 1 , an electrode 2 connected in series with the solar cell sheet 2 , a pair of encapsulating films 3 sandwiching the solar cell sheet 1 and the electrode 2 , and being disposed on the solar energy The glass plate 5 on the front side of the battery sheet and the back plate 4 disposed on the reverse side of the solar cell sheet 1 are disposed, and the pair of packaging films 3 are interposed between the glass plate 5 and the back plate 4. The electrode 2 may be a copper-tin alloy, but is not limited thereto and may be other suitable metals or alloys. The encapsulation film 3 completely covers the periphery of the solar cell sheet 1 and the electrode 2. The material of the encapsulation film 3 of the present embodiment is usually ethylene vinyl acetate (EVA), and the material of the back sheet 4 is usually polyvinyl fluoride (PVF), such as DuPont TM Tedlar. . In some embodiments, the backsheet 4 can be a composite layer comprising two PVF layers 4a with a polyester layer sandwiched between the two layers.
接著,對太陽能電池模組100進行分段式加熱,其中分段式加熱包括兩段式或更多段式加熱,且可直接在空氣中加熱而不需通入其他氣體。本發明是利用分段加熱先分離封裝膜3及背板4,再加以燃燒並碳化。如果僅採用單段式的加熱,因太陽能電池模組100中的封裝膜3被背板4及玻璃板5包夾住,封裝膜3在燃燒時將受到背板4的阻礙,因而對於模組100的結構造成應力,產生例如玻璃板5破碎等問題。本案發明人發現採用分段式加熱,先將封裝膜3及背板4分離,後續再進行封裝膜3及背板4的燃燒碳化,將可降低加熱時模組100所承受的應力,以分離完整的模組100的其他構成。Next, the solar cell module 100 is subjected to sectional heating, wherein the segmented heating includes two-stage or more-stage heating, and can be directly heated in the air without passing other gases. In the present invention, the encapsulating film 3 and the backing plate 4 are separated by segment heating, and then burned and carbonized. If only one-stage heating is used, since the package film 3 in the solar cell module 100 is sandwiched by the back plate 4 and the glass plate 5, the package film 3 will be hindered by the back plate 4 when burned, and thus the module is The structure of 100 causes stress, causing problems such as breakage of the glass plate 5. The inventor of the present invention found that by using segmented heating, the encapsulating film 3 and the backing plate 4 are separated first, and then the combustion carbonization of the encapsulating film 3 and the backing plate 4 is performed, which can reduce the stress on the module 100 during heating to separate. The other components of the complete module 100.
在一實施例中,可進行兩段式加熱,且其中第一段的溫度低於第二段的溫度。在一些進行兩段式加熱的實施例中,先於330-380℃的溫度下加熱太陽能電池模組100以分離封裝膜3及背板4。封裝膜3及背板4的分離是藉由背板4的分解燃燒、掀起,甚至結構破裂以暴露出封裝膜3來達成。此段加熱的時間可為至少10分鐘,較佳為約10-30分鐘。接著,升高加熱溫度至400-450℃並在此溫度下加熱太陽能電池模組100以同時燃燒碳化封裝膜3及背板4。此段加熱的時間可為至少2小時,較佳為2-3小時。在另一實施例中,也可將第二段加熱進一步分成兩段,其中先於400-420℃加熱約1-1.5小時以碳化背板4,再於420-450℃加熱約1-3.5小時以碳化封裝膜3,因此上述三段式加熱藉由在第二、第三段加熱的不同溫度下分別碳化為不同材質的背板4、封裝膜3,使背板4、封裝膜3的燃燒碳化更為完全。雖然上述是以兩段或三段式加熱為例進行說明,但此技藝人示可依照封裝膜3及背板4材質的受熱特性調整溫度並選擇合適的加熱段數,使得加熱時模組100的結構受到最小的應力,而可在後續得到完整的太陽能電池模組100的其他各個組成。In one embodiment, two-stage heating can be performed, and wherein the temperature of the first stage is lower than the temperature of the second stage. In some embodiments in which two-stage heating is performed, the solar cell module 100 is heated at a temperature of 330-380 ° C to separate the encapsulation film 3 and the back sheet 4. The separation of the encapsulating film 3 and the backing plate 4 is achieved by decomposition combustion, pick-up, and even structural cracking of the backing plate 4 to expose the encapsulating film 3. This period of heating can be at least 10 minutes, preferably about 10-30 minutes. Next, the heating temperature is raised to 400-450 ° C and the solar cell module 100 is heated at this temperature to simultaneously burn the carbonized encapsulating film 3 and the back sheet 4. This period of heating can be at least 2 hours, preferably 2-3 hours. In another embodiment, the second stage heating can be further divided into two sections, wherein the heating is performed at 400-420 ° C for about 1-1.5 hours to carbonize the back sheet 4, and then heated at 420-450 ° C for about 1-3.5 hours. The encapsulating film 3 is carbonized, so that the three-stage heating is performed by carbonizing the back sheet 4 and the encapsulating film 3 of different materials at different temperatures of the second and third stages of heating to burn the back sheet 4 and the encapsulating film 3. Carbonization is more complete. Although the above description is based on two-stage or three-stage heating, the skilled person can adjust the temperature according to the heating characteristics of the material of the package film 3 and the back plate 4 and select a suitable number of heating sections so that the module 100 is heated. The structure is subjected to minimal stress, and other various components of the completed solar cell module 100 can be obtained later.
在加熱太陽能電池模組100並且完全燃燒碳化封裝膜3及背板4之後,用水清洗太陽能電池模組100以移除加熱過程中產生的灰份。此時已完成封裝膜3及背板4的分解及移除,並分離出太陽能電池片1、焊條2、及玻璃板5。如果分離出太陽能電池片1、焊條2、及玻璃板5上仍殘留有灰份,可再用水清洗。特別注意的是,在本發明之實施例中,可得到完整的玻璃板5,清洗後乾淨且完整的玻璃板5直接重複使用於新的太陽能電池模組。回收的焊條2在重新使用前可能需要額外的加工處理,例如可再分離純化以得到乾淨的金屬材料。另外,因為在本發明實施例中,因加熱的溫度較低(低於先前技術US 6,063,995所使用之約480-520℃的加熱溫度),而較不容易有雜質熱擴散進入太陽能電池片1及玻璃板5,因此太陽能電池片1及玻璃板5遭受的污染較少。After the solar cell module 100 is heated and the carbonized encapsulation film 3 and the back sheet 4 are completely burned, the solar cell module 100 is washed with water to remove ash generated during the heating process. At this time, the decomposition and removal of the package film 3 and the back sheet 4 are completed, and the solar cell sheet 1, the electrode 2, and the glass sheet 5 are separated. If the ash content remains on the solar cell sheet 1, the electrode 2, and the glass plate 5, it can be washed with water. It is particularly noted that in the embodiment of the invention, a complete glass sheet 5 is obtained, and the clean and intact glass sheet 5 after cleaning is directly reused in the new solar cell module. The recovered electrode 2 may require additional processing prior to reuse, such as re-separation and purification to obtain a clean metal material. In addition, in the embodiment of the present invention, since the heating temperature is low (lower than the heating temperature of about 480-520 ° C used in the prior art US 6,063,995), it is less likely to have impurities thermally diffuse into the solar cell sheet 1 and The glass sheet 5, therefore, the solar cell sheet 1 and the glass sheet 5 are less contaminated.
太陽能電池片1包括晶片,例如矽晶片,其上通常形成有金屬電極、抗反射層、金屬導線及射極層。金屬電極的材料可為例如鋁。抗反射層的材料可為例如SiNx 。導線的材料可為例如銀。要得到可回收利用的晶片,需先將晶片上的金屬電極、抗反射層、金屬導線移除,但並不限定移除的順序。可利用酸液蝕刻清洗晶片以移除金屬電極,例如80℃鹽酸/過氧化氫(HCl/H2 O2 )之混合水溶液。亦可利用酸液蝕刻清洗晶片以移除抗反射層及金屬導線,例如氫氟酸(HF)溶液。可利用鹼液蝕刻清洗晶片以移除射極層,例如80℃氫氧化鈉(NaOH)溶液。最後,將晶片以清水洗淨後,即可在矽晶生長中作為原料使用。The solar cell sheet 1 comprises a wafer, such as a germanium wafer, on which metal electrodes, anti-reflective layers, metal wires and emitter layers are typically formed. The material of the metal electrode may be, for example, aluminum. The material of the antireflection layer may be, for example, SiN x . The material of the wire can be, for example, silver. In order to obtain a recyclable wafer, the metal electrode, the anti-reflection layer, and the metal wire on the wafer are first removed, but the order of removal is not limited. The wafer can be cleaned by acid etching to remove a metal electrode such as a mixed aqueous solution of hydrochloric acid/hydrogen peroxide (HCl/H 2 O 2 ) at 80 °C. The wafer can also be cleaned by acid etching to remove the anti-reflective layer and metal wires, such as a hydrofluoric acid (HF) solution. The wafer can be cleaned with an lye etch to remove the emitter layer, such as a 80 ° C sodium hydroxide (NaOH) solution. Finally, after the wafer is washed with water, it can be used as a raw material in twin growth.
本發明的回收程序可以解決太陽能電池模組廢棄物的產生問題,可適用於許多不同類型的電池模組。本發明方法先透過分段式加熱簡單有效地燃燒碳化EVA與PVF,在移除EVA與PVF之後,可得到太陽能電池片、焊條、及未破碎且完整的玻璃板,其中玻璃板可以直接再次拿來封裝電池模組。分離出的太陽能電池片經過適當蝕刻清洗可以得到乾淨的矽晶片,可作為長晶原料使用。此外分離得到的焊條,可再經純化得到乾淨的金屬材料。The recycling program of the present invention can solve the problem of solar cell module waste generation and can be applied to many different types of battery modules. The method of the invention firstly and efficiently burns the carbonized EVA and the PVF through the segmented heating. After removing the EVA and the PVF, the solar cell sheet, the welding rod, and the unbroken and complete glass plate can be obtained, wherein the glass plate can be taken directly again. To package the battery module. The separated solar cell sheet can be cleaned by appropriate etching to obtain a clean tantalum wafer, which can be used as a long crystal material. In addition, the separated electrode can be purified to obtain a clean metal material.
本發明之實施例還具有下列優點:(1)選用的加熱溫度較低,因此可減少焊條破裂、焊條與矽反應、及雜質擴散進入矽晶片與玻璃板的可能性,因此矽晶片的純度與原始晶片相當,可以作為長晶原料使用;(2)分段式的熱處理溫度可以避免玻璃板因為過大的熱應力而碎裂,因此所得到的玻璃板與封裝前的玻璃板完全相同,不需要經過重鑄即可直接使用,適合大面積以及大量的模組回收程序使用;(3)可在空氣中進行加熱而不需通入惰性氣體,回收成本較低亦沒有排氣灰份過高而難以處理的問題產生,製程中產生的灰份是使用清水清洗來移除,清洗後的汙水可經由沉降來進行淨化,因此實施在大量製程上的可行性較高。Embodiments of the present invention also have the following advantages: (1) the selected heating temperature is low, thereby reducing the possibility of electrode cracking, electrode and bismuth reaction, and diffusion of impurities into the ruthenium wafer and the glass plate, so the purity of the ruthenium wafer is The original wafer is equivalent and can be used as a long-crystal raw material; (2) The segmented heat treatment temperature can prevent the glass plate from being broken due to excessive thermal stress, so the obtained glass plate is exactly the same as the glass plate before packaging, and does not need It can be used directly after recasting, suitable for large-area and large-scale module recycling procedures; (3) It can be heated in the air without introducing inert gas, and the recovery cost is low and the exhaust ash is too high. The problem that is difficult to handle is that the ash generated in the process is removed by washing with clean water, and the cleaned sewage can be purified by sedimentation, so that it is highly feasible to implement in a large number of processes.
【比較例1:單段式加熱】[Comparative Example 1: Single-stage heating]
提供一尺寸為200 mm x 200mm的矽晶太陽能電池模組,其具有如第2圖所示之結構,包括:太陽能電池片、焊條、封裝膜、背板、玻璃板、鋁框與接線盒,且其中封裝膜使用EVA材料,背板使用DuPontTM Tedlar材料。將鋁框與接線盒拆除回收。將移除鋁框與接線盒之後的矽晶太陽能電池模組置入加熱爐。將加熱爐內溫度升高至約480℃,並在此溫度下加熱矽晶太陽能電池模組1小時。A silicon solar cell module having a size of 200 mm x 200 mm is provided, which has the structure as shown in Fig. 2, including: solar cell sheet, electrode, encapsulation film, back sheet, glass plate, aluminum frame and junction box, And the encapsulation film uses EVA material and the back plate uses DuPont TM Tedlar material. Remove the aluminum frame and junction box. The silicon solar cell module after removing the aluminum frame and the junction box is placed in the heating furnace. The temperature in the furnace was raised to about 480 ° C, and the twin solar cell module was heated at this temperature for 1 hour.
將矽晶太陽能電池模組從加熱爐取出,並以清水清洗矽晶太陽能電池模組以移除加熱過程中所產生的灰份,此時可分離出焊條、太陽能電池片、及玻璃板。以清水清洗分離出的各部分上殘留的灰份。The twin crystal solar cell module is taken out from the heating furnace, and the twin crystal solar cell module is cleaned with water to remove the ash generated during the heating process, and the electrode, the solar cell sheet, and the glass plate can be separated at this time. The remaining ash on each part separated is washed with water.
為得到乾淨的矽晶片,將太陽能電池片作以下的處理。先以體積比例為1:1:5的80℃鹽酸(HCl濃度37%)/過氧化氫(H2 O2 濃度31%)/水之混合水溶液清洗太陽能電池片以移除鋁金屬電極。接著,以5%的氫氟酸(HF)水溶液清洗太陽能電池片以移除SiNx 抗反射層及銀導線。最後,以80℃的25%氫氧化鈉(NaOH)水溶液清洗太陽能電池片以移除射極層(emitter layer)。In order to obtain a clean tantalum wafer, the solar cell wafer was subjected to the following treatment. The solar cell was first washed with a mixed solution of 80 ° C hydrochloric acid (HCl concentration 37%) / hydrogen peroxide (H 2 O 2 concentration 31%) / water in a volume ratio of 1:1:5 to remove the aluminum metal electrode. Next, the solar cell sheet was washed with a 5% aqueous solution of hydrofluoric acid (HF) to remove the SiN x antireflection layer and the silver wire. Finally, the solar cell was washed with a 25% aqueous solution of sodium hydroxide (NaOH) at 80 ° C to remove the emitter layer.
觀察處理後所分離出來的矽晶太陽能電池模組的各部分,發現有下列情況:分離出的玻璃板破裂且遭受污染、焊條品質劣化、及矽晶片遭受污染。Observation of each part of the twin solar cell module separated after the treatment revealed that the separated glass plate was broken and contaminated, the quality of the electrode was deteriorated, and the wafer was contaminated.
【實施例1:三段式加熱】[Example 1: Three-stage heating]
提供一尺寸為200 mm x 200 mm的矽晶太陽能電池模組,其具有如第2圖所示之結構,包括太陽能電池片、焊條、封裝膜、背板、玻璃板、鋁框與接線盒,且其中封裝膜使用EVA材料,背板使用DuPontTM Tedlar材料。將鋁框與接線盒拆除回收。將移除鋁框與接線盒之後的矽晶太陽能電池模組置入加熱爐。將加熱爐內溫度升高至約380℃,並在此溫度下加熱矽晶太陽能電池模組30分鐘以分離封裝膜3及背板4。接著將加熱爐內溫度升高至約400℃,並在此溫度下加熱矽晶太陽能電池模組1小時以碳化背板4。再將加熱爐內溫度升高至約420℃,並在此溫度下加熱矽晶太陽能電池模組2小時以碳化封裝膜3。第3圖顯示本實施例之三段式加熱的溫度變化示意圖。A silicon solar cell module measuring 200 mm x 200 mm is provided, which has a structure as shown in Fig. 2, including a solar cell sheet, an electrode, a packaging film, a back sheet, a glass plate, an aluminum frame and a junction box. And the encapsulation film uses EVA material and the back plate uses DuPont TM Tedlar material. Remove the aluminum frame and junction box. The silicon solar cell module after removing the aluminum frame and the junction box is placed in the heating furnace. The temperature in the heating furnace was raised to about 380 ° C, and the twinned solar cell module was heated at this temperature for 30 minutes to separate the encapsulating film 3 and the back sheet 4. Next, the temperature in the heating furnace was raised to about 400 ° C, and the twinned solar cell module was heated at this temperature for 1 hour to carbonize the back sheet 4. The temperature in the heating furnace was further raised to about 420 ° C, and the twinned solar cell module was heated at this temperature for 2 hours to carbonize the encapsulating film 3. Fig. 3 is a view showing the temperature change of the three-stage heating of the present embodiment.
加熱完成後,封裝膜3及背板4已完全被碳化分解。將矽晶太陽能電池模組從加熱爐取出,並以清水清洗矽晶太陽能電池模組以移除加熱過程中所產生的灰份,此時可分離出焊條、太陽能電池片、及玻璃板,其中玻璃板為未破裂且完整的。以清水清洗分離出的各部分上殘留的灰份。After the heating is completed, the encapsulating film 3 and the back sheet 4 are completely decomposed by carbonization. The twin crystal solar cell module is taken out from the heating furnace, and the twin crystal solar cell module is cleaned with water to remove the ash generated during the heating process, and the electrode, the solar cell sheet, and the glass plate can be separated at this time, wherein The glass plate is unbroken and intact. The remaining ash on each part separated is washed with water.
為得到乾淨的矽晶片,將太陽能電池片作以下的處理。先以體積比例為1:1:5的80℃鹽酸(HCl濃度37%)/過氧化氫(H2 O2 濃度31%)/水之混合水溶液清洗太陽能電池片以移除鋁金屬電極。接著,以5%氫氟酸(HF)水溶液清洗太陽能電池片以移除SiNx 抗反射層及銀導線。最後,以80℃的25%氫氧化鈉(NaOH)水溶液清洗太陽能電池片以移除射極層。經上述處理後,可得到乾淨的矽晶片。In order to obtain a clean tantalum wafer, the solar cell wafer was subjected to the following treatment. The solar cell was first washed with a mixed solution of 80 ° C hydrochloric acid (HCl concentration 37%) / hydrogen peroxide (H 2 O 2 concentration 31%) / water in a volume ratio of 1:1:5 to remove the aluminum metal electrode. Next, the solar cell sheet was washed with a 5% aqueous solution of hydrofluoric acid (HF) to remove the SiN x antireflection layer and the silver wire. Finally, the solar cell was washed with a 25% aqueous solution of sodium hydroxide (NaOH) at 80 ° C to remove the emitter layer. After the above treatment, a clean tantalum wafer can be obtained.
使用輝光放電質譜檢測儀(glow-discharge mass spectroscopy,GDMS)測量所得矽晶片之純度,表1顯示矽晶片中各雜質的濃度。The purity of the obtained tantalum wafer was measured using a glow-discharge mass spectroscopy (GDMS), and Table 1 shows the concentration of each impurity in the tantalum wafer.
第4圖顯示矽晶片所含金屬雜質濃度相對於標準化效率的關係圖,其中標示出矽晶片所能容忍鈦、鐵、鋁的濃度,其中鈦濃度低於10-5 ppmw、鐵濃度低於2×10-3 ppmw、鋁濃度低於2×10-2 ppmw。本發明實施例1中處理後之晶片含有0.02 ppmw的鈦、0.09 ppmw的鐵、及0.07 ppmw的鋁,而根據偏析理論,鈦、鐵、鋁的偏析係數分別為kTi =3.2×10-6 、kFe =6.4×10-6 、kAl =2.8×10-3 ,本發明實施例1之晶片回收經過熔化並重新生長成晶體後,鈦、鐵、鋁的濃度將會分別降低至6.4×10-8 ppmw、5.8×10-7 ppmw、5.6×10-5 ppmw,而由第4圖可知,此回收材料經過重新生長晶體後所含雜質對最後製作的電池效率幾乎沒有影響。Figure 4 shows the relationship between the concentration of metal impurities contained in the germanium wafer versus the normalized efficiency, which indicates that the concentration of titanium, iron, and aluminum can be tolerated by the germanium wafer, wherein the titanium concentration is lower than 10 -5 ppmw and the iron concentration is lower than 2 ×10 -3 ppmw, aluminum concentration is less than 2 × 10 -2 ppmw. The wafer processed in the first embodiment of the present invention contains 0.02 ppmw of titanium, 0.09 ppmw of iron, and 0.07 ppmw of aluminum, and according to the segregation theory, the segregation coefficients of titanium, iron, and aluminum are respectively k Ti = 3.2 × 10 -6 . , k Fe = 6.4 × 10 -6 , k Al = 2.8 × 10 -3 , after the wafer recovery of the first embodiment of the present invention is melted and re-grown into crystals, the concentrations of titanium, iron and aluminum will be reduced to 6.4×, respectively. 10 -8 ppmw, 5.8 × 10 -7 ppmw, 5.6 × 10 -5 ppmw, and as can be seen from Fig. 4, the impurities contained in the recycled material after re-growing the crystal have little effect on the efficiency of the final fabricated battery.
觀察處理後所分離出來的矽晶太陽能電池模組的各部分,不僅玻璃板及焊條為未破裂且完整的,晶片及玻璃板所受的污染相較於比較例1也較小。因此經上述處理後所分離出來的矽晶太陽能電池模組的各部分,具有較好的完整性且遭受較少的污染。Observing the parts of the twin solar cell module separated after the treatment, not only the glass plate and the electrode were unbroken and intact, but also the contamination of the wafer and the glass plate was smaller than that of Comparative Example 1. Therefore, the portions of the twinned solar cell module separated by the above treatment have better integrity and suffer less pollution.
【實施例2:二段式加熱】[Example 2: Two-stage heating]
提供一尺寸為200 mm x 200 mm的矽晶太陽能電池模組,其具有如第2圖所示之結構,包括:太陽能電池片、焊條、封裝膜、背板、玻璃板、鋁框與接線盒,且其中封裝膜使用EVA材料,背板使用DuPontTM Tedlar材料。將鋁框與接線盒拆除回收。將移除鋁框與接線盒之後的矽晶太陽能電池模組置入加熱爐。將加熱爐內溫度升高至約330℃,並在此溫度下加熱矽晶太陽能電池模組10分鐘以分離封裝膜3及背板4。再將加熱爐內溫度升高至約400℃,並在此溫度下加熱矽晶太陽能電池模組2小時以碳化封裝膜3及背板4。第5圖顯示本實施例之二段式加熱的溫度變化示意圖。A silicon solar cell module measuring 200 mm x 200 mm is provided, which has the structure as shown in Fig. 2, including: solar cell sheet, electrode, encapsulation film, back sheet, glass plate, aluminum frame and junction box And the encapsulation film uses EVA material and the back plate uses DuPont TM Tedlar material. Remove the aluminum frame and junction box. The silicon solar cell module after removing the aluminum frame and the junction box is placed in the heating furnace. The temperature in the heating furnace was raised to about 330 ° C, and the twinned solar cell module was heated at this temperature for 10 minutes to separate the encapsulating film 3 and the back sheet 4. Then, the temperature in the heating furnace was raised to about 400 ° C, and the twinned solar cell module was heated at this temperature for 2 hours to carbonize the encapsulating film 3 and the backing plate 4. Fig. 5 is a view showing the temperature change of the two-stage heating of the present embodiment.
加熱完成後,封裝膜3及背板4已完全被碳化分解。將矽晶太陽能電池模組從加熱爐取出,並以清水清洗矽晶太陽能電池模組以移除加熱過程中所產生的灰份,此時可分離出焊條、太陽能電池片、及玻璃板,其中玻璃板為未破裂且完整的。以清水清洗分離出的各部分上殘留的灰份。After the heating is completed, the encapsulating film 3 and the back sheet 4 are completely decomposed by carbonization. The twin crystal solar cell module is taken out from the heating furnace, and the twin crystal solar cell module is cleaned with water to remove the ash generated during the heating process, and the electrode, the solar cell sheet, and the glass plate can be separated at this time, wherein The glass plate is unbroken and intact. The remaining ash on each part separated is washed with water.
為得到乾淨的矽晶片,將太陽能電池片作以下的處理。先以體積比例為1:1:5的80℃鹽酸(HCl濃度37%)/過氧化氫(H2 O2 濃度31%)/水之混合水溶液清洗太陽能電池片以移除鋁金屬電極。接著,以5%氫氟酸(HF)水溶液清洗太陽能電池片以移除SiNx 抗反射層及銀導線。最後,以80℃的25%氫氧化鈉(NaOH)水溶液清洗太陽能電池片以移除射極層。經上述處理後,可得到乾淨的矽晶片。In order to obtain a clean tantalum wafer, the solar cell wafer was subjected to the following treatment. The solar cell was first washed with a mixed solution of 80 ° C hydrochloric acid (HCl concentration 37%) / hydrogen peroxide (H 2 O 2 concentration 31%) / water in a volume ratio of 1:1:5 to remove the aluminum metal electrode. Next, the solar cell sheet was washed with a 5% aqueous solution of hydrofluoric acid (HF) to remove the SiN x antireflection layer and the silver wire. Finally, the solar cell was washed with a 25% aqueous solution of sodium hydroxide (NaOH) at 80 ° C to remove the emitter layer. After the above treatment, a clean tantalum wafer can be obtained.
使用輝光放電質譜檢測儀(glow-discharge mass spectroscopy,GDMS)測量所得矽晶片之純度,表2顯示矽晶片中各雜質的濃度。The purity of the obtained tantalum wafer was measured using a glow-discharge mass spectroscopy (GDMS), and Table 2 shows the concentration of each impurity in the tantalum wafer.
同樣地,可參照第4圖而找出本發明實施例2中處理後之矽晶片所含鈦、鐵、鋁之濃度對於矽晶片的效率的影響。本發明實施例2中處理後之晶片含有僅含有0.18ppmw的金屬鋁雜質,而根據偏析理論,鋁的偏析係數為kAl =2.8×10-3 ,因此本發明實施例2之晶片回收經過熔化並重新生長成晶體後,鋁濃度將會降低至5.1×10-5 ppmw。比照後可得知,處理後的矽晶片所含鋁之濃度對其效率幾乎沒有影響。Similarly, the influence of the concentration of titanium, iron, and aluminum contained in the germanium wafer after the treatment in the second embodiment of the present invention on the efficiency of the germanium wafer can be found with reference to FIG. The wafer processed in the second embodiment of the present invention contains only 0.18 ppmw of metal aluminum impurities, and according to the segregation theory, the segregation coefficient of aluminum is k Al = 2.8 × 10 -3 , so the wafer recovery of the second embodiment of the present invention is melted. After re-growth into crystals, the aluminum concentration will decrease to 5.1 × 10 -5 ppmw. It can be seen from the comparison that the concentration of aluminum contained in the treated germanium wafer has little effect on its efficiency.
觀察處理後所分離出來的矽晶太陽能電池模組的各部分,不僅玻璃板及焊條為未破裂且完整的,矽晶片及玻璃板所受的污染相較於比較例1也較小。因此經上述處理後所分離出來的矽晶太陽能電池模組的各部分,具有較好的完整性且遭受較少的污染。Observing the parts of the twinned solar cell module separated after the treatment, not only the glass plate and the electrode were unbroken and intact, but also the contamination of the silicon wafer and the glass plate was smaller than that of Comparative Example 1. Therefore, the portions of the twinned solar cell module separated by the above treatment have better integrity and suffer less pollution.
因此,由實驗證實本發明之使用分段式加熱的太陽能電池模組回收方法,可分離出較完整且較不受污染的太陽能電池模組的各部分,特別是可分離出較不受污染的玻璃板及晶片,且其中玻璃板為完整的玻璃板,因而可直接被重新使用。Therefore, it has been experimentally confirmed that the method for recovering the solar cell module using the segmented heating of the present invention can separate the parts of the relatively complete and less polluting solar cell module, in particular, can be separated from the pollution-free Glass plates and wafers, and in which the glass plate is a complete glass plate, can be directly reused.
雖然本發明已以數個較佳實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
100...太陽能電池模組100. . . Solar battery module
1...太陽能電池片1. . . Solar cell
2...焊條2. . . welding rod
3...封裝膜3. . . Encapsulation film
4、4a、4b...背板4, 4a, 4b. . . Backplane
5...玻璃板5. . . glass plate
10、20、30、40、50、60...步驟10, 20, 30, 40, 50, 60. . . step
第1圖顯示根據於本發明實施例之太陽能電池模組回收流程示意圖。FIG. 1 is a schematic view showing a recycling process of a solar cell module according to an embodiment of the present invention.
第2圖顯示一太陽能電池模組100的剖面示意圖。FIG. 2 shows a schematic cross-sectional view of a solar cell module 100.
第3圖顯示實施例1之三段式加熱的溫度變化示意圖。Fig. 3 is a view showing the temperature change of the three-stage heating of Example 1.
第4圖顯示本發明實施例中處理後之矽晶片所含金屬雜質濃度相對於標準化效率的關係圖。Fig. 4 is a graph showing the relationship between the concentration of metal impurities contained in the germanium wafer after the treatment in the embodiment of the present invention with respect to the normalization efficiency.
第5圖顯示實施例2之二段式加熱的溫度變化示意圖。Fig. 5 is a view showing the temperature change of the two-stage heating of Example 2.
10、20、30、40、50、60...步驟10, 20, 30, 40, 50, 60. . . step
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