skip to main content

DOE PAGESDOE PAGES

Title: Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van der Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [5] ; ORCiD logo [4] ; ORCiD logo [6] ; ORCiD logo [2] ; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Xi'an Jiaotong Univ., Xi'an (China). Frontier Inst. of Science and Technology jointly with College of Science, State Key Lab. for Mechanical Behavior of Materials
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Nanyang Technological Univ. (Singapore). Center for Programmable Materials, School of Materials Science and Engineering
Publication Date:
Report Number(s):
BNL-114187-2017-JA
Journal ID: ISSN 1530-6984; R&D Project: 16060; 16060; KC0403020
Grant/Contract Number:
SC0012704; AC02-06CH11357; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 9; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; copper sulfide; Nanoflake; lithium ion battery; Center for Functional Nanomaterials; CuS; electrochemistry kinetics; in situ TEM
OSTI Identifier:
1376191