| 研究生: |
李庭萱 Li, Ting-Hsuan |
|---|---|
| 論文名稱: |
以濕法冶金原理回收廢鋰電池中有價金屬之研究 Hydrometallurgical Process for the Recovery of Valuable Metals from Spent Lithium-ion Batteries |
| 指導教授: |
申永輝
Shen, Yun-Hwei |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 資源工程學系 Department of Resources Engineering |
| 論文出版年: | 2019 |
| 畢業學年度: | 107 |
| 語文別: | 中文 |
| 論文頁數: | 72 |
| 中文關鍵詞: | 廢鋰離子電池 、浸漬 、離子交換 、選擇性化學沉澱 |
| 外文關鍵詞: | Spent Li-ion Battery, leaching, ion exchange, chemical precipitation |
| 相關次數: | 點閱:91 下載:3 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
隨著科技發展迅速,人類對於生活品質及需求逐年增長,而現今社會隨處可見與鋰電池相關的產品,因此廢棄鋰電池相關處理及再利用之研究開發有其重要性。本研究以離子交換與化學沉澱法分離鋰、鈷、錳、鎳等有價金屬,以利後續回收高純度的金屬產物。
本實驗分為三階段,第一階段將鋰電池中陰極材料進行前處理及特性分析,了解原料成分及晶相結構,有利於後續研究規劃。第二階段為探討酸浸漬之實驗參數,尋找最佳浸漬參數,其實驗結果顯示使用濃度為6 N 之硫酸、固液比70 g/L、添加5 vol.% H2O2,於反應溫度60 ℃之環境下反應3小時,其鋰、鈷、錳、鎳之浸漬率皆達90 %以上。
第三階段為利用選擇性化學沉澱及離子交換進行有價金屬分離回收。首先,將浸漬液進行硫化沉澱,使鈷、鎳完全沉澱與溶液中有價金屬鋰、錳分離,之後分為兩個部分進行有價金屬回收。第一部分:利用化學沉澱法,以碳酸鈉作為沉澱劑,將鋰、錳分離回收,得到碳酸錳與碳酸鋰之沉澱物,其錳、鋰之產物純度分別為87、70 %;第二部分:先使用鹽酸將硫化沉澱後之產物硫化鈷及硫化鎳溶解,所得之鈷鎳溶液藉由離子交換樹脂進行吸附,以達到鈷、鎳分離。吸附後之樹脂利用濃鹽酸溶液去除殘留液,再以清水進行解析,達成鈷之分離與純化,其回收鈷之純度為99 %。
With the rapid development of science and technology, human beings have grown their quality of life and demand year by year. Nowadays, lithium-ion battery-related products can be seen everywhere in society. Therefore, the research and development of disposal and reuse of waste lithium batteries are of great importance. In this study, ion exchange and chemical precipitation were used to separate valuable metals. The experiment is divided into three stages. In the first stage, the cathode material in the lithium battery is pretreated and characterized to understand the composition of the raw materials and the crystal phase structure. The second stage is to investigate the experimental parameters of acid leaching. The experimental results show that the reaction is carried out for 3 hours at a reaction temperature of 60 °C using a sulfuric acid concentration of 6 N, a solid-liquid ratio of 70 g/L, and addition of 5 vol.% H2O2. The leaching efficiency of lithium, cobalt, manganese, and nickel are all above 90%. The third stage is the separation and recovery of valuable metals by chemical precipitation and ion exchange. Lithium and manganese are separated and recovered by using sodium carbonate as a precipitating agent. The purity of the manganese and lithium products were 87% and 70%, respectively. Finally, adsorption by ion exchange resin to achieve separation of cobalt and nickel. The recovered cobalt has a purity of 99%.
[1]L. Chen, X. Tang, Y. Zhang, L. Li, Z. Zeng, and Y. Zhang, "Process for the recovery of cobalt oxalate from spent lithium-ion batteries," Hydrometallurgy, vol. 108, no. 1-2, pp. 80-86, 2011.
[2]L. Li, R. Chen, F. Sun, F. Wu, and J. Liu, "Preparation of LiCoO2 films from spent lithium-ion batteries by a combined recycling process," Hydrometallurgy, vol. 108, no. 3-4, pp. 220-225, 2011.
[3]X. Zeng, J. Li, and Y. Ren, "Prediction of various discarded lithium batteries in China," in IEEE International Symposium on Sustainable Systems and Technology (ISSST), 2012, pp. 1-4
[4]P. Meshram, B. Pandey, and T. Mankhand, "Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching," Chemical Engineering Journal, vol. 281, pp. 418-427, 2015.
[5]A. Nayl, R. Elkhashab, S. M. Badawy, and M. El-Khateeb, "Acid leaching of mixed spent Li-ion batteries," Arabian Journal of Chemistry, vol. 10, pp. S3632-S3639, 2017.
[6]H. Wen zhi et al., "Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation," Transactions of Nonferrous Metals Society of China, vol. 22, no. 9, pp. 2274-2281, 2012.
[7]A. Nayl, M. M. Hamed, and S. Rizk, "Selective extraction and separation of metal values from leach liquor of mixed spent Li-ion batteries," Journal of the Taiwan Institute of Chemical Engineers, vol. 55, pp. 119-125, 2015.
[8]許荏賓, "溶劑萃取分離廢二次鋰電池有價金屬," 朝陽科技大學環境工程與管理系學位論文, pp. 1-78, 2016.
[9]鄭如翔和黃炳照, "鋰離子電池正極材料之發展," 化工, vol. 58, no. 5, pp. 10-39, 2011.
[10]B. L. Ellis, K. T. Lee, and L. F. Nazar, "Positive electrode materials for Li-ion and Li-batteries," Chemistry of materials, vol. 22, no. 3, pp. 691-714, 2010.
[11]X. Chen, Y. Chen, T. Zhou, D. Liu, H. Hu, and S. Fan, "Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries," Waste Manag, vol. 38, pp. 349-56, Apr 2015.
[12]林月微, "高性能電池正極材料介紹," 工業材料, vol. 157, p. 153, 2000.
[13]劉如熹, "鋰離子二次電池材料簡介," 化學, vol. 57, no. 2, pp. 149-150, 1999.
[14]V. Etacheri, R. Marom, R. Elazari, G. Salitra, and D. Aurbach, "Challenges in the development of advanced Li-ion batteries: a review," Energy & Environmental Science, vol. 4, no. 9, pp. 3243-3262, 2011.
[15]O. E. Bankole, C. Gong, and L. Lei, "Battery recycling technologies: Recycling waste lithium ion batteries with the impact on the environment in-view," Journal of Environment and Ecology, vol. 4, no. 1, pp. 14-28, 2013.
[16]李洪枚和姜亢, "廢舊鋰離子電池對環境污染的分析與對策," 上海環境科學, vol. 23, no. 5, 2004.
[17]何星融, "鋰三元電池廢正極材料有價金屬再生之研究," 國立成功大學資源工程所, 2018.
[18]陳奕瑄, "廢鋰電池中有價金屬資源化研究," 碩士, 資源工程學系碩博士班, 國立成功大學, 台南市, 2018.
[19]李洪桂, "濕法冶金學," 中南大學出版社, 2005, pp. 30-35.
[20]國立台灣大學化學系有機教研小組, 大學有機化學實驗 (no. 7). 國立台灣大學出版中心, 2004.
[21]葉子維, "分離廢鋰離子電池中有價金屬之研究,"碩士, 資源工程學系碩博士班, 國立成功大學, 台南市, 2018.
[22]蘇英源和郭金國, "冶金學,"全華圖書股份有限公司, 2001.
[23]N. Takeno, "Atlas of Eh-pH Diagrams, Intercomparison of Thermodynamic Databases.," National Institute of Advanced Industrial Science and Technology, no. 419, 2005.
[24]J. Ortiz-Landeros, C. Gómez-Yáñez, R. López-Juárez, I. Dávalos-Velasco, and H. Pfeiffer, "Synthesis of advanced ceramics by hydrothermal crystallization and modified related methods," Journal of Advanced Ceramics, vol. 1, no. 3, pp. 204-220, 2012.
[25]C. D. Tsakiroglou, K. Hajdu, K. Terzi, C. Aggelopoulos, and M. Theodoropoulou, "A statistical shrinking core model to estimate the overall dechlorination rate of PCE by an assemblage of zero-valent iron nanoparticles," Chemical Engineering Science, vol. 167, pp. 191-203, 2017.
[26]V. Safari, G. Arzpeyma, F. Rashchi, and N. Mostoufi, "A shrinking particle—shrinking core model for leaching of a zinc ore containing silica," International journal of mineral processing, vol. 93, no. 1, pp. 79-83, 2009.
[27]C. Dickinson and G. Heal, "Solid–liquid diffusion controlled rate equations," Thermochimica Acta, vol. 340, pp. 89-103, 1999.
[28]H.-l. SUN, H.-y. YU, B. WANG, Y. MIAO, G.-f. TU, and S.-w. BI, "Leaching dynamics of 12CaO· 7Al 2 O 3," The Chinese Journal of Nonferrous Metals, vol. 18, no. 10, pp. 1920-1925, 2008.
[29]D. Dutta et al., "Close loop separation process for the recovery of Co, Cu, Mn, Fe and Li from spent lithium-ion batteries," Separation and Purification Technology, vol. 200, pp. 327-334, 2018.
[30]L. Li et al., "Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching," Waste Manag, vol. 71, pp. 362-371, Jan 2018.
[31]S. M. Shin, N. H. Kim, J. S. Sohn, D. H. Yang, and Y. H. Kim, "Development of a metal recovery process from Li-ion battery wastes," Hydrometallurgy, vol. 79, no. 3-4, pp. 172-181, 2005.
[32]B. Swain, J. Jeong, J.-c. Lee, G.-H. Lee, and J.-S. Sohn, "Hydrometallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries," Journal of Power Sources, vol. 167, no. 2, pp. 536-544, 2007.
[33]J. Nan, D. Han, M. Yang, M. Cui, and X. Hou, "Recovery of metal values from a mixture of spent lithium-ion batteries and nickel-metal hydride batteries," Hydrometallurgy, vol. 84, no. 1-2, pp. 75-80, 2006.
[34]R.-C. Wang, Y.-C. Lin, and S.-H. Wu, "A novel recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries," Hydrometallurgy, vol. 99, no. 3-4, pp. 194-201, 2009.
[35]P. Zhang, T. Yokoyama, O. Itabashi, T. M. Suzuki, and K. Inoue, "Hydrometallurgical process for recovery of metal values from spent lithium-ion secondary batteries," Hydrometallurgy, vol. 47, no. 2-3, pp. 259-271, 1998.
[36]M. Contestabile, S. Panero, and B. Scrosati, "A laboratory-scale lithium-ion battery recycling process," Journal of Power Sources, vol. 92, no. 1-2, pp. 65-69, 2001.
[37]S. Castillo, F. Ansart, C. Laberty-Robert, and J. Portal, "Advances in the recovering of spent lithium battery compounds," Journal of Power Sources, vol. 112, no. 1, pp. 247-254, 2002.
[38]C. K. Lee and K.-I. Rhee, "Preparation of LiCoO2 from spent lithium-ion batteries," Journal of Power Sources, vol. 109, no. 1, pp. 17-21, 2002.
[39]C. K. Lee and K.-I. Rhee, "Reductive leaching of cathodic active materials from lithium ion battery wastes," Hydrometallurgy, vol. 68, no. 1-3, pp. 5-10, 2003.
[40]K.-L. Chiu and W.-S. Chen, "Recovery and Separation of Valuable Metals from Cathode Materials of Spent Lithium-Ion Batteries (LIBs) by Ion Exchange," Science of Advanced Materials, vol. 9, no. 12, pp. 2155-2160, 2017.
[41]F. Mendes and A. Martins, "Selective nickel and cobalt uptake from pressure sulfuric acid leach solutions using column resin sorption," International Journal of Mineral Processing, vol. 77, no. 1, pp. 53-63, 2005.
[42]Z. Zainol and M. J. Nicol, "Ion-exchange equilibria of Ni2+, Co2+, Mn2+ and Mg2+ with iminodiacetic acid chelating resin Amberlite IRC 748," Hydrometallurgy, vol. 99, no. 3-4, pp. 175-180, 2009.
[43]Y. Song and Z. Zhao, "Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques," Separation and Purification Technology, vol. 206, pp. 335-342, 2018.