自廢二次鋰電池正極材料以超音波分離錳及微乳液法分離鈷與鎳

Ultrasonic Separation of Manganese and Microemulsion Separation of Nickel and Lithium from Cathode Materials of spent Lithium-ion Battery

許政凱(JENG-KAI HSU)

指導教授 ： 王文裕

朝陽科技大學/理工學院/環境工程與管理系/碩士(2016年)

摘要

國內目前回收的廢鋰電池皆採境外輸出處理。以往之化學沉澱法應用在新型三元系鋰電池回收時，因鈷、錳、鎳三金屬共沉澱，導致回收金屬資源之純度與價值大減。本研究探討三元系鋰電池正極材料之超音波輔助酸溶，及微乳液萃取。
本研究酸溶實驗，在不加雙氧水的情況下進行超音波輔助酸溶，比較Mn及Co/Ni/Li的溶出率。微乳液萃取用以分離Co及Ni/Li，選用表面活性劑溴化十六烷基三甲銨(CTMAB, cetyltrimethylammonium bromide)、助表面活性劑正戊醇、有機相正庚烷，及外水相硫氰酸銨(NH4SCN, Ammoniutn Thiocyanate)溶液來製備微乳液。
結果顯示，鍛燒前處理及提高酸當量，對超音波輔助酸溶之金屬溶出效率無顯著差異。金屬溶出率由高至低，分別為採用超音波增幅器、超音波振盪槽，最低者為磁石攪拌機(無超音波輔助)。採用超音波振盪槽輔助酸溶，比原採用磁石攪拌方式所需之雙氧水量大幅減少80%。採用超音波增幅器輔助溶出正極材料時，錳未溶出，酸溶浸漬液為Co/Ni/Li溶液。可以超音波增幅器分離錳，及鈷與鎳。
微乳液萃取分離Co及Ni/Li，在30秒內即可達到平衡。萃取作用為放熱反應，升高操作溫度並未提升萃取率。透過改變實驗條件發現鈷萃取率可達62%，而Ni和Li之萃取率在5%以下；採用二次萃取鈷萃取率可達98%，鎳與鋰之萃取率保持在5%以下。

關鍵字

酸溶 ； 超音波 ； 微乳液 ； 鈷 ； 鎳

並列摘要

At present the battery recovery plants in Taiwan only reclaim manganese batteries and alkaline zinc-manganese dioxide batteries. The spent lithium-ion batteries are all exported outside the border. When chemical precipitation method was employed to recovery metals from the new type of NMC (LiNiO2/LiCoO2/LiMn2O4) lithium-ion batteries the three metals co-precipitated and produced a low value material. This study investigated the ultrasound assisted acid dissolution and microemulsion extraction for cathode material of NMC lithium-ion battery.
This study compared the differences of Mn and Co/Ni/Li dissolution ratios between ultrasound assistance and non-ultrasound assistance in acid solution without addition of hydrogen peroxide. Microemulsion extraction was accomplished to separate Co and Ni/Li with CTMAB (cetyltrimethylammonium bromide) as surfactant, n-pentanol as cosurfactant, n-heptance as organic phase, and NH4SCN(Ammoniutn Thiocyanate) as outer water phase.
The experiment results reveal that pre-calcination and higher acid concentrations have no obvious effect upon dissolution ratios of metals. On the hand, ultrasonic booster, ultrasonic bath and magnetic stirrer have high, middle and low improvement on metal dissolution ratios, respectively. Comparing with magnetic stirrer, ultrasonic bath can reduce 80% addition amounts of hydrogen peroxide for dissolution of metals. When using ultrasonic booster, Mn was no dissolution and the acid solution contained only Co/Ni/Li. Separation of Mn and Co/Ni/Li can be accomplished by using Ultrasonic booster
Microemulsion extraction was used to separation of Co and Ni, and extraction reached equilibrium in 30 seconds. Microemulsion extraction is an exothermic reaction. Increasing operating temperatures will not improve the extraction efficiency. The optimum operation results showed the extraction ratio of Co was 62%, and the extraction ratios of Ni and Li were all below 5%. Using two stages extraction, the extraction ratio of Co can reach 98%, and the extraction ratios of Ni and Li were all below 5%.

並列關鍵字

Acid soluble ； Ultrasound ； Microemulsion ； Cobalt ； Nickel

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