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  • 學位論文

從廢棄CIGS太陽能電池回收硒、鎵、銦之研究

Recycling of Selenium, Gallium, and Indium from Waste CIGS Solar Cell

指導教授 : 駱尚廉
本文將於2026/06/29開放下載。若您希望在開放下載時收到通知,可將文章加入收藏

摘要


近年來溫室效應的加劇以及化石能源的匱乏,使得各國政府急需尋找更清潔的能源。在這種背景條件下,取之不盡用之不竭的太陽能源就獲得了各國政府的青睞。而太陽能電池的大量應用,就會產生大量的光伏電池廢棄物。所以太陽能電池的回收技術,也需要受到重視。 當前占據光伏市場主體的是晶矽太陽能電池,晶矽太陽能電池是第一代太陽能電池。剩下的市場則被第二代太陽能電池——薄膜太陽能電池所占據。目前市場上,薄膜太陽能電池主要分爲兩類,一類是碲化鎘(Cadmium Telluride, CdTe)太陽能電池;另一類是銅銦鎵硒(Copper Indium Gallium Selenide, CIGS)太陽能電池。CIGS太陽能電池的光吸收層是由銅、銦、鎵、硒四個元素組成,如果能夠有效回收這些元素,能夠使CIGS太陽能電池更加符合環保要求,也能讓CIGS太陽能電池產業更有競爭力。 本研究使用微波熱裂解的方式來做前處理,目的是去除廢棄CIGS太陽能電池表面的有機材質;再使用高溫氧化法來分離回收硒元素;最後使用高溫氯化法來逐步分離和回收鎵元素與銦元素。 在微波熱裂解的過程中以200 W的微波功率,將手工裁剪後的CIGS太陽能電池板在氮氣的氛圍下加熱1 h。使得樣品失重率達到90%以上,最終溫度穩定在330 ℃左右,再將樣品研磨成粉末。使用微波熱裂解後的樣品,在純氧環境下以800 ℃氧化1 h,用去離子水吸收尾氣中的二氧化硒,從而達到回收硒元素的目的。再將去硒後剩下的殘渣混合氯化銨,在氮氣的氛圍下加熱至260 ℃~540 ℃,同樣用去離子水吸收尾氣中的鎵銦氯化物,從而達到回收鎵元素與銦元素的目的。 本研究之結果顯示,使用微波熱裂解作爲前處理能夠有效去除CIGS太陽能電池表面的有機質,並且能夠大幅度提升銅、銦、鎵、硒等元素在樣品中的含量,並且微波加熱相比較傳統電加熱有更好的加熱效率。在硒回收實驗中,僅需要600 ℃氧化30 min即可回收99%的硒元素。在鎵銦回收實驗中,不同溫度下鎵銦回收有明顯的先後順序,可以通過控制溫度來分步分離鎵元素與銦元素。 本研究的回收方法對比傳統的酸浸出回收金屬法,最大的優勢是不會有大量的強酸性廢液產生,並且有較好的回收效率。未來應有機會能夠應用在工業生產中,對於環境也相對較爲友好。

並列摘要


In recent years, governments need a clean energy urgently because of greenhouse effect and energy crisis. Because the solar energy is an inexhaustible source of energy for human beings, it is a good choice to replace fossil energy. However, using a large of solar cells will produce a large of cell waste. Therefore, technology of recycling from waste solar cells needs to be developed. Currently, the main photovoltaic market is occupied by crystalline silicon solar cells. This solar cell is the first generation of solar cells. Other market is occupied by thin film solar cells, or the second generation of solar cells. They include Cadmium Telluride (CdTe) soler cells and Copper Indium Gallium Selenide (CIGS) soler cells. Absorption layer of CIGS is made by elements of Cu, In, Ga, and Se. If they can be recovered effectively, CIGS solar cells industry can be more competitive. In this study, microwave-enhanced pyrolysis was used as pretreatment to remove the organic materials from the surface of CIGS. Then, the high temperature oxidation was used to separate selenium. Finally, the high temperature chlorination was performed to separate gallium and indium gradually. In microwave-enhanced pyrolysis process, the hand-cut CIGS solar cells were heated in nitrogen for 1 hour at 200 W microwave power. The weight loss rate of samples needs higher than 90%, and the final temperature is about 330 ℃. Then the samples were ground into powder. After pretreatment, the samples were oxidized at 800 ℃ for 1 hour in the oxygen. Selenium dioxide was absorbed by deionized water from exhaust gas. After removal of selenium, the samples were mixed with ammonium chloride and heated to 260 ℃~540 ℃ in nitrogen for 2 hours. Chlorinated gallium and indium were also absorbed by deionized water form exhaust gas. These processes achieve recycling of selenium, gallium and indium. The result of this study shows that microwave-enhanced pyrolysis as a pretreatment can remove the organic materials from the surface of CIGS solar cells effectively. Also, it can increase the concentration of copper, indium, gallium, and selenium significantly. Comparing with electric heating, microwave heating was more efficient. In selenium recovery, only 30 mins of oxidation at 600 ℃ is required to recover 99% of selenium. Another result in gallium and indium recovery is that different metals were recovered in different temperature. So, gallium and indium can be separated step by step by controlling the temperature. Comparing with conventional acid leaching method, the advantage of this method is that it does not produce a large amount of strongly acidic waste solution. And it has a good recovery efficiency relatively. This study is an environmentally friendly technique for the recover gallium, indium, and selenium from CIGS solar cells. It will be used in industry possibly.

參考文獻


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