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《科学通报(英文版)》 2018-18
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Electrochemical solid-state amorphization in the immiscible Cu-Li system

Muhua Sun;Jiake Wei;Zhi Xu;Qianming Huang;Yu Zhao;Wenlong Wang;Xuedong Bai;Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences;School of Physical Sciences, University of Chinese Academy of Sciences;  
As a typical immiscible binary system, copper (Cu) and lithium (Li) show no alloying and chemical intermixing under normal circumstances. Here we show that, when decreasing Cu nanoparticle sizes into ultrasmall range, the nanoscale size effect can play a subtle yet critical role in mediating the chemical activity of Cu and therefore its miscibility with Li, such that the electrochemical alloying and solidstate amorphization will occur in such an immiscible system. This unusual observation was accomplished by performing in-situ studies of the electrochemical lithiation processes of individual CuO nanowires inside a transmission electron microscopy (TEM). Upon lithiation, CuO nanowires are first electrochemically reduced to form discrete ultrasmall Cu nanocrystals that, unexpectedly, can in turn undergo further electrochemical lithiation to form amorphous Cu Lixnanoalloys. Real-time TEM imaging unveils that there is a critical grain size (ca. 6 nm), below which the nanocrystalline Cu particles can be continuously lithiated and amorphized. The possibility that the observed solid-state amorphization of Cu-Li might be induced by electron beam irradiation effect can be explicitly ruled out; on the contrary, it was found that electron beam irradiation will lead to the dealloying of as-formed amorphous Cu Lixnanoalloys.
【Fund】: supported by the National Natural Science Foundation of China (11474337 51472267 21773303 and 51421002);; the Program by Chinese Academy of Sciences (ZDYZ2015-1 and XDB07030100);; Austrian-Chinese Cooperative R&D Projects FFG and Chinese Academy of Sciences (112111KYSB20150002)
【CateGory Index】: TG146.11
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