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Title: Morphology-Controlled Discharge Profile and Reversible Cu Extrusion and Dissolution in Biomimetic CuS

Abstract

Metal sulfides, such as CuS, SnS2, Co9S8, MoS2, are high capacity anode materials for Li-ion batteries. However, these materials go through a conversion reaction with Li+, which is accompanied by the phase transformation and inevitably results in a huge volume expansions, therefore causing performance degradation. Here, we report nanoscale engineering route to efficiently control the overall volume expansion for enhanced performance. We engineered CuS with nanoplate assembly on a nanostring, leading to a nanostructure of mimicking the crassula baby necklace (CBN) in the natural plant. Using in-situ transmission electron microscopy (in-situ TEM), we probed the lithiation kinetics and dynamic structural transformations. Due to the linkage of the central nanostring, the CuS CBN exhibited fast Li+ diffusion along the axial direction and high mechanical stability during lithiation. The volume expansion was minimal for the CuS CBN due to the pre-engineered gap between these plates. The CuS followed a two-step lithiation process with Cu2S and Li2S formation as the first step and Cu extrusion from Cu2S in the later stage. Interestingly, during the Cu2S to Cu conversion, there was a incubation period before the metallic Cu extrusion, which is featured by the formation of an amorphous structure due to the large latticemore » strain and distortion associated with the displacement of Cu by Li ions. In the final stage, the lithiated amorphous phase recrystallized to a composite of Cu nanocrystals dispersed in a polycrystalline Li2S matrix. Associate with the nanoscale size, the Cu nanocrystals can reversibly dissolve into the matrix upon delithiation. The present work demonstrates tailoring of desired functionality through nanoscale engineering of using bionic methods.« less

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Materials Science and Engineering, Southern University of Science and Technology, No. 1088 Xueyuan Boulevard, Shenzhen, Guangdong 518055, China
  2. Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1496753
Report Number(s):
PNNL-SA-138373
Journal ID: ISSN 1944-8244
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 48; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Han, Shaobo, Wang, Jing, Shi, Xiaobo, Guo, Mohan, Wang, Hong, Wang, Chongmin, and Gu, Meng. Morphology-Controlled Discharge Profile and Reversible Cu Extrusion and Dissolution in Biomimetic CuS. United States: N. p., 2018. Web. doi:10.1021/acsami.8b17387.
Han, Shaobo, Wang, Jing, Shi, Xiaobo, Guo, Mohan, Wang, Hong, Wang, Chongmin, & Gu, Meng. Morphology-Controlled Discharge Profile and Reversible Cu Extrusion and Dissolution in Biomimetic CuS. United States. doi:10.1021/acsami.8b17387.
Han, Shaobo, Wang, Jing, Shi, Xiaobo, Guo, Mohan, Wang, Hong, Wang, Chongmin, and Gu, Meng. Wed . "Morphology-Controlled Discharge Profile and Reversible Cu Extrusion and Dissolution in Biomimetic CuS". United States. doi:10.1021/acsami.8b17387.
@article{osti_1496753,
title = {Morphology-Controlled Discharge Profile and Reversible Cu Extrusion and Dissolution in Biomimetic CuS},
author = {Han, Shaobo and Wang, Jing and Shi, Xiaobo and Guo, Mohan and Wang, Hong and Wang, Chongmin and Gu, Meng},
abstractNote = {Metal sulfides, such as CuS, SnS2, Co9S8, MoS2, are high capacity anode materials for Li-ion batteries. However, these materials go through a conversion reaction with Li+, which is accompanied by the phase transformation and inevitably results in a huge volume expansions, therefore causing performance degradation. Here, we report nanoscale engineering route to efficiently control the overall volume expansion for enhanced performance. We engineered CuS with nanoplate assembly on a nanostring, leading to a nanostructure of mimicking the crassula baby necklace (CBN) in the natural plant. Using in-situ transmission electron microscopy (in-situ TEM), we probed the lithiation kinetics and dynamic structural transformations. Due to the linkage of the central nanostring, the CuS CBN exhibited fast Li+ diffusion along the axial direction and high mechanical stability during lithiation. The volume expansion was minimal for the CuS CBN due to the pre-engineered gap between these plates. The CuS followed a two-step lithiation process with Cu2S and Li2S formation as the first step and Cu extrusion from Cu2S in the later stage. Interestingly, during the Cu2S to Cu conversion, there was a incubation period before the metallic Cu extrusion, which is featured by the formation of an amorphous structure due to the large lattice strain and distortion associated with the displacement of Cu by Li ions. In the final stage, the lithiated amorphous phase recrystallized to a composite of Cu nanocrystals dispersed in a polycrystalline Li2S matrix. Associate with the nanoscale size, the Cu nanocrystals can reversibly dissolve into the matrix upon delithiation. The present work demonstrates tailoring of desired functionality through nanoscale engineering of using bionic methods.},
doi = {10.1021/acsami.8b17387},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 48,
volume = 10,
place = {United States},
year = {2018},
month = {10}
}