從鋰離子二次電池中回收有價值金屬之新方法

A Novel Recovery Process of Metal Values from Spent Lithium-ion Secondary Batteries

林育全(Yu-Chuan Lin)

指導教授 ： 王榮基

大同大學/工程學院/化學工程學系所/碩士(2008年)

摘要

本實驗係以LiCoO2、LiMn2O4及LiCo1/3Ni1/3Mn1/3O2為材料，模擬鋰離子二次電池之陰極以分離回收鈷、鎳、錳和鋰。在4M的鹽酸、溫度80oC、時間1小時、、固液比1/50 g/ml時，鈷、錳、鎳和鋰的酸溶率可達到99%。使用KMnO4可有選擇性的完全分離回收出二氧化錳和氫氧化錳。接著使用dimethylglyoxime可由溶液分離出鎳。過濾後的濾液使用1M的氫氧化鈉，使其pH值達到11，接著使用過濾的方法就可分離出鈷。最後使用飽和的碳酸鈉溶液於100oC下回收剩下的鋰離子。
使用回收出的氫氧化鈷和氫氧化錳物質，以合成LiCoO2和LiMn2O4作為鋰離子二次電極之陰極材料，並測定其電化學性質。

關鍵字

酸溶 ； 回收 ； 鋰離子二次電池

並列摘要

The simulated experiments with the separation and recovery of metal values such as cobalt, manganese, nickel and lithium from spent lithium-ion secondary batteries were studied. A leaching efficiency of more than 99% of cobalt, manganese, nickel and lithium could be achieved with 4 M HCl solution, 80 oC leaching temperature, 1 h leaching time and 1/50 g/ml solid-to-liquid ratio. The manganese in the leaching liquor was reacted selectively and nearly completely with KMnO4 reagent, then the manganese was recovered as MnO2 and manganese hydroxide. The nickel in the leaching liquor was adsorbed selectively and nearly completely with dimethylglyoxime. An addition of 1M NaOH solution to reach pH=11 allowed the selective precipitation of cobalt hydroxides. The remaining lithium in the aqueous solution was readily recovered as lithium carbonate precipitate by the addition of a saturated sodium carbonate solution. The recovery of cobalt and manganese hydroxides would be used to synthesize LiCoO2 and LiMn2O4 as a cathode in a common lithium-ion battery configuration. The performance of the electrochemical properties was also tested.

並列關鍵字

leaching ； recovery ； lithium-ion secondary batteries

參考文獻

Arena, F., G. Trunfio, J. Negro, B. Fazio and L. Spadaro, ‘‘Basic Evidence of the Molecular Dispersion of MnCeOx Catalysts Synthesized via a Novel “Redox-Precipitation” Route,’’ Chem. Mater., 19, 2269-2276 (2007).

Armstrong, A.R., Bruce and G. Peter, ‘‘Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries,’’ Nature (London), 381(6582), 499-500 (1996).

Belharouak, I., Y.K. Sun, J. Liu, and K. Amine, ‘‘Li(Ni1/3Co1/3Mn1/3)O2 as a suitable cathode for high power applications,’’ Journal of Power Sources, 123(2), 247-252 (2003).

Bernardes, A.M., D.C.R. Espinosa and J.A.S. Tenorino, ‘‘Recycling of batteries: a review of current processes and technologies,’’ Journal of Power Sources, 130, 291-298 (2004).

Bok, J.S., J.H. Lee, B.K. Lee, D.P. Kim, J.S. Rho, H.S. Yang and K.S. Han, ‘‘Effects of synthetic conditions on electrochemical activity of LiCoO2prepared from recycled cobalt compounds,’’ Solid State Ionics , 169, 139-144 (2004).