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Title: In situ TEM probing of crystallization form-dependent sodiation behavior in ZnO nanowires for sodium-ion batteries

Development of sodium-ion battery (SIB) electrode materials currently lags behind electrodes in commercial lithium-ion batteries (LIBs). However, in the long term, development of SIB components is a valuable goal. Their similar, but not identical, chemistries require careful identification of the underlying sodiation mechanism in SIBs. Here in this study, we utilize in situ transmission electron microscopy to explore quite different sodiation behaviors even in similar electrode materials through real-time visualization of microstructure and phase evolution. Upon electrochemical sodiation, single-crystalline ZnO nanowires (sc-ZNWs) are found to undergo a step-by-step electrochemical displacement reaction, forming crystalline NaZn 13 nanograins dispersed in a Na 2O matrix. This process is characterized by a slowly propagating reaction front and the formation of heterogeneous interfaces inside the ZNWs due to non-uniform sodiation amorphization. In contrast, poly-crystalline ZNWs (pc-ZNWs) exhibited an ultrafast sodiation process, which can partly be ascribed to the availability of unobstructed ionic transport pathways among ZnO nanograins. Thus the reaction front and heterogeneous interfaces disappear. The in situ TEM results, supported by calculation of the ion diffusion coefficient, provide breakthrough insights into the dependence of ion diffusion kinetics on crystallization form. This points toward a goal of optimizing the microstructure of electrode materials in ordermore » to develop high performance SIBs.« less
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [4] ;  [2] ;  [5] ;  [2] ;  [3]
  1. Southeast Univ., Nanjing (China). Key Lab. of MEMS of the Ministry of Education, SEU-FEI Nano-Pico Center; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  2. Southeast Univ., Nanjing (China). Key Lab. of MEMS of the Ministry of Education, SEU-FEI Nano-Pico Center
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics
Publication Date:
Report Number(s):
BNL-113854-2017-JA
Journal ID: ISSN 2211-2855; R&D Project: MA015MACA; KC0201010
Grant/Contract Number:
SC0012704; AC02-98CH10886; SC0012704l
Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 30; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; Sodium-ion batteries; In situ transmission electron microscopy; ZnO nanowires; Electrochemical sodiation; Microstructure control
OSTI Identifier:
1372427
Alternate Identifier(s):
OSTI ID: 1419585