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Title: Atomic-Scale Observation of Electrochemically Reversible Phase Transformations in SnSe2 Single Crystals

Abstract

2D materials have shown great promise to advance next-generation lithium-ion battery technology. Specifically, tin-based chalcogenides have attracted widespread attention because lithium insertion can introduce phase transformations via three types of reactions—intercalation, conversion, and alloying—but the corresponding structural changes throughout these processes, and whether they are reversible, are not fully understood. Here, the first real-time and atomic-scale observation of reversible phase transformations is reported during the lithiation and delithiation of SnSe2 single crystals, using in situ high-resolution transmission electron microscopy complemented by first-principles calculations. Lithiation proceeds sequentially through intercalation, conversion, and alloying reactions (SnSe2 → LixSnSe2 → Li2Se + Sn → Li2Se + Li17Sn4) in a manner that maintains structural and crystallographic integrity, whereas delithiation forms numerous well-aligned SnSe2 nanodomains via a homogeneous deconversion process, but gradually loses the coherent orientation in subsequent cycling. Furthermore, alloying and dealloying reactions cause dramatic structural reorganization and thereby consequently reduce structural stability and electrochemical cyclability, which implies that deep discharge for Sn chalcogenide electrodes should be avoided. Overall, the findings elucidate atomistic lithiation and delithiation mechanisms in SnSe2 with potential implications for the broader class of 2D metal chalcogenides.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States); Clemson Univ., SC (United States)
  2. Northwestern Univ., Evanston, IL (United States); Harvard Univ., Cambridge, MA (United States)
  3. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1543461
Alternate Identifier(s):
OSTI ID: 1479535
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 51; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemistry; Science & Technology - Other Topics; Materials Science; Physics

Citation Formats

Kim, Sungkyu, Yao, Zhenpeng, Lim, Jin-Myoung, Hersam, Mark C., Wolverton, Chris, Dravid, Vinayak P., and He, Kai. Atomic-Scale Observation of Electrochemically Reversible Phase Transformations in SnSe2 Single Crystals. United States: N. p., 2018. Web. doi:10.1002/adma.201804925.
Kim, Sungkyu, Yao, Zhenpeng, Lim, Jin-Myoung, Hersam, Mark C., Wolverton, Chris, Dravid, Vinayak P., & He, Kai. Atomic-Scale Observation of Electrochemically Reversible Phase Transformations in SnSe2 Single Crystals. United States. doi:10.1002/adma.201804925.
Kim, Sungkyu, Yao, Zhenpeng, Lim, Jin-Myoung, Hersam, Mark C., Wolverton, Chris, Dravid, Vinayak P., and He, Kai. Thu . "Atomic-Scale Observation of Electrochemically Reversible Phase Transformations in SnSe2 Single Crystals". United States. doi:10.1002/adma.201804925. https://www.osti.gov/servlets/purl/1543461.
@article{osti_1543461,
title = {Atomic-Scale Observation of Electrochemically Reversible Phase Transformations in SnSe2 Single Crystals},
author = {Kim, Sungkyu and Yao, Zhenpeng and Lim, Jin-Myoung and Hersam, Mark C. and Wolverton, Chris and Dravid, Vinayak P. and He, Kai},
abstractNote = {2D materials have shown great promise to advance next-generation lithium-ion battery technology. Specifically, tin-based chalcogenides have attracted widespread attention because lithium insertion can introduce phase transformations via three types of reactions—intercalation, conversion, and alloying—but the corresponding structural changes throughout these processes, and whether they are reversible, are not fully understood. Here, the first real-time and atomic-scale observation of reversible phase transformations is reported during the lithiation and delithiation of SnSe2 single crystals, using in situ high-resolution transmission electron microscopy complemented by first-principles calculations. Lithiation proceeds sequentially through intercalation, conversion, and alloying reactions (SnSe2 → LixSnSe2 → Li2Se + Sn → Li2Se + Li17Sn4) in a manner that maintains structural and crystallographic integrity, whereas delithiation forms numerous well-aligned SnSe2 nanodomains via a homogeneous deconversion process, but gradually loses the coherent orientation in subsequent cycling. Furthermore, alloying and dealloying reactions cause dramatic structural reorganization and thereby consequently reduce structural stability and electrochemical cyclability, which implies that deep discharge for Sn chalcogenide electrodes should be avoided. Overall, the findings elucidate atomistic lithiation and delithiation mechanisms in SnSe2 with potential implications for the broader class of 2D metal chalcogenides.},
doi = {10.1002/adma.201804925},
journal = {Advanced Materials},
number = 51,
volume = 30,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
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Figures / Tables:

Figure-1 Figure-1: a) Schematic illustration of a single crystalline SnSe2 nanoflakes using the mechanical exfoliation method. The in situ TEM samples are mounted onto a half TEM grid and the metal wire to observe phase transformation of SnSe2 along the planar and cross-section directions, respectively. b) Schematics of in situ TEMmore » experiment setup showing the half-cell battery operated at potentiostatic mode (details see Experimental Section). c) TEM image, d) electron diffraction pattern, and e) enlarged HRTEM images of the pristine SnSe2 nanoflake. f) TEM image showing the electrochemical contact between the vertically mounted SnSe2 nanoflakes and the Li electrode. g) The interlayer spacing of (001) plane at the pristine state. h) Time-lapse HRTEM images showing phase transformation of SnSe2 throughout the lithiation process. i) Plot of the interlayer spacing change, and j) time-lapse HRTEM images upon Li intercalation but before amorphization (Movie S1). The red lines and blue circles indicate the bending of SnSe2 (001) planes and the migration of Li-ions, respectively.« less

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