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Enhanced Electrochemical Performance of Ultracentrifugation-Derived nc-Li3VO4/MWCNT Composites for Hybrid Supercapacitors

机译:超离心衍生的nc-Li3VO4 / MWCNT复合材料在混合超级电容器中的电化学性能增强

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摘要

Nanocrystalline Li3VO4 dispersed within multiwalled carbon nanotubes (MWCNTs) was prepared using an ultracentrifugation (uc) process and electrochemically characterized in Li-containing electrolyte. When charged and discharged down to 0.1 V vs Li, the material reached 330 mAh g–1 (per composite) at an average voltage of about 1.0 V vs Li, with more than 50% capacity retention at a high current density of 20 A g–1. This current corresponds to a nearly 500C rate (7.2 s) for a porous carbon electrode normally used in electric double-layer capacitor devices (1C = 40 mA g–1 per activated carbon). The irreversible structure transformation during the first lithiation, assimilated as an activation process, was elucidated by careful investigation of in operando X-ray diffraction and X-ray absorption fine structure measurements. The activation process switches the reaction mechanism from a slow “two-phase” to a fast “solid-solution” in a limited voltage range (2.5–0.76 V vs Li), still keeping the capacity as high as 115 mAh g–1 (per composite). The uc-Li3VO4 composite operated in this potential range after the activation process allows fast Li+ intercalation/deintercalation with a small voltage hysteresis, leading to higher energy efficiency. It offers a promising alternative to replace high-rate Li4Ti5O12 electrodes in hybrid supercapacitor applications.
机译:使用超速离心(uc)工艺制备了分散在多壁碳纳米管(MWCNT)中的纳米晶Li3VO4,并在含锂的电解质中进行了电化学表征。当对Li进行低至0.1 V的充电和放电时,该材料在大约1.0 V vs Li的平均电压下达到330 mAh g–1(每个复合材料),在20 A g的高电流密度下容量保持率超过50% –1。对于双电层电容器设备中通常使用的多孔碳电极,此电流对应于接近500C的速率(7.2 s)(每个活性炭1C = 40 mA g-1)。通过仔细研究操作中的X射线衍射和X射线吸收精细结构测量,阐明了第一次锂化过程中不可逆的结构转变(被称为激活过程)。激活过程在有限的电压范围内(2.5–0.76 V vs Li)将反应机理从缓慢的“两相”切换为快速的“固溶”,仍保持高达115 mAh g–1的容量(每个复合)。活化过程后,在此电位范围内运行的uc-Li3VO4复合材料可实现快速的Li +嵌入/脱嵌,并具有较小的电压滞后,从而提高了能效。它为在混合超级电容器应用中替代高速率Li4Ti5O12电极提供了有希望的替代方法。

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