为了恢复锂离子电池中正极钴酸锂材料的电化学活性，对置于LiOH溶液中的失效钴酸锂进行超声再生研究。采用 XRD 和 Raman 光谱分析钴酸锂晶体结构，采用 SEM 分析钴酸锂表面形貌和颗粒大小，采用 FT-IR光谱仪和 TGA 热分析仪分析钴酸锂表面粘附的有机物。结果表明：超声空化效应可以有效地去除钴酸锂表面的有机物，并有利于钴酸锂晶体在LiOH溶液中Co和Li阳离子的重排。室温条件下，失效的钴酸锂在2.0 mol/L LiOH溶液中经过12 h超声处理后，成功恢复了其电化学活性。锂离子电池的首次充电容量为132.2 mA?h/g，首次放电容量为131.9 mA?h/g，第50次循环时的电容保持率为97.2%。
The spent LiCoO 2 was treated in LiOH solution exerted by ultrasound with the aim to renovate its electrochemical characteristics. The crystal structures of LiCoO2 were characterized by XRD and Raman spectroscopy, respectively. The morphology and particle sizes of LiCoO2 were analyzed by SEM. The organic substance adhered to the used LiCoO2 particle surfaces was determined by using Fourier transform infrared spectrometer (FT-IR) and thermogravimetric analysis (TGA), respectively. The results show that ultrasonic cavitation can be effectively used to remove organic substance stuck on LiCoO2 surface and facilitate the cation rearrangement of Co+ and Li+ in LiOH. At room temperature, the spent LiCoO2 is successfully renovated in 2.0 mol/L LiOH solution treated by ultrasound for 12 h. The charge capacity in the first cycle is 132.2 mA?h/g, the discharge capacity is 131.9 mA?h/g, and 97.2% of the discharge capacity is retained after 50 cycles.
参考文献
| [1] | ARMAND M, TARASCON J M. Building better batteries[J]. Nature, 2008, 451:652-657.,2008. |
| [2] | LI L, LU J, REN Y, ZHANG X X, CHEN R J, WU F, AMINE K. Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. J Power Sources, 2012, 218:21-27.,2012. |
| [3] | LI L, DUNN J B, ZHANG X X, GAINES L, CHEN R J, WU F, AMINE K. Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment[J]. J Power Sources, 2013, 233:180-189.,2013. |
| [4] | SUN L, QIU K. Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries[J]. Waste Management, 2012, 32(8):1575-1582.,2012. |
| [5] | ZHU S G, HE W Z, LI G M, X. ZHOU, ZHANG X J, HUANG J W. Recovery of Co and Li from spent lithium-ion batteries by the combination method of acid leaching and chemical precipitation[J]. Transaction of Nonferrous Metals Society of China, 2012, 22(9):2274-2281.,2012. |
| [6] | 潘晓勇,彭玲,陈伟华,韦泽平,卢潇,陈正,王婕.废旧锂离子电池中钴和锂的回收及综合利用[J].中国有色金属学报,2013(07):2047-2054. |
| [7] | PAULINO J F, BUSNARDO N G, AFONSO J C. Recovery of valuable elements from spent Li-batteries[J]. J Hazard Mater, 2008, 150:843-849.,2008. |
| [8] | LIU Yun-jian,HU Qi-yang,LI Xin-hai,WANG Zhi-xing,GUO Hua-jun.Recycle and synthesis of LiCoO2 from incisors bound of Li-ion batteries[J].中国有色金属学会会刊（英文版）,2006(04):956-959. |
| [9] | BAHAT M, FARGHALY F E, ABDEL BASIR S M, FOUAD O A. Synthesis, characterization and magnetic properties of microcrystalline lithium cobalt ferrite from spent lithium-ion batteries[J]. Journal of Materials Processing Technology, 2007, 183:117-121.,2007. |
| [10] | 周旭,朱曙光,次西拉姆,贺文智,李光明,黄菊文.废锂离子电池负极材料的机械分离与回收[J].中国有色金属学报,2011(12):3082-3086. |
| [11] | LI J G, ZHAO R S, HE X M, LIU H. Preparation of LiCoO2 cathode materials from spent lithium-ion batteries[J]. Ionics, 2009, 15:111-113.,2009. |
| [12] | GOPUKUMAR S, JEONG Y, KIM K B. Synthesis and electrochemical performance of tetravalent doped LiCoO 2 lithium rechargeable cells[J]. Solid State Ionics, 2003, 159(3/4):223-232. in,2003. |
| [13] | ZOU M J, YOSHIO M, GOPUKUMAR S, YAMAKI J I. Synthesis of high-voltage(4.5 V)cycling doped LiCoO 2 for use in lithium rechargeable cells[J]. Chemistry of Materials, 2003, 15(25):4699-4702.,2003. |
| [14] | DAHN J R, SACKEN U, MICHAL A R. Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni(OH)2 structure[J]. Solid State Ionics, 1990, 44(1/2):87-97.,1990. |
| [15] | LUO X F, WANG X Y, LIAO L, GAMBOA S, SEBASTIAN P J. Synthesis and characterization of high tap-density layered Li【Ni 1/3Co1/3Mn1/3】O2 cathode material via hydroxide co-precipitation[J]. J Power Sources, 2006, 158(1):654-658.,2006. |
| [16] | GUPTA R, MANTHIRAM A. Chemical extraction of lithium from layered LiCoO 2 [J]. Journal of Solid State Chemistry, 1996, 121(2):483-491.,1996. |
| [17] | WU F, WANG M, SU Y F, BAO L Y, CHEN S. A novel method for synthesis of layered LiNi 1/3Mn1/3Co1/3O2 as cathode material for lithium-ion battery[J]. J Power Sources, 2010, 195(8):2362-2367.,2010. |
| [18] | 吕文广.高结晶度钴酸锂制备及微结构表征[J].稀有金属快报,2004(12):30-33. |
| [19] | 王志远,崔宏祥,万均,赵乾.废旧锂离子电池正极材料钴酸锂层状结构的活化研究[J].天津理工大学学报,2008(05):5-8. |
| [20] | 符娟,刘彩云,刘照军,余红静,莫育俊.锂离子电池正极材料LiCoO2在电池充放电过程中结构变化的谱学研究[J].光散射学报,2009(01):52-58. |
| [21] | INABA M, IRIYAMA Y, OGUMI Z, TODZUKA Y, TASAKA A. Raman study of layered rock-salt LiCoO 2 and its electrochemical lithium deintercalation[J]. Raman Spectroscopy, 1997, 28(8):613-617.,1997. |
| [22] | MENDOZA L, BADDOUR-HADJEAN R, CASSIR M, PEREIRA-RAMOS J P. Raman evidence of the formation of LT-LiCoO 2 thin 1ayers on NiO in molten carbonate at 650℃[J]. Applied Surface Science, 2004, 225(1/4):356-361.,2004. |
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