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Title: Probing the mechanism of sodium ion insertion into copper antimony Cu2Sb anodes

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp501032d· OSTI ID:1159405
 [1];  [2];  [3];  [3];  [1];  [1];  [3];  [4];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of California, San Diego, La Jolla, CA (United States)
  3. Univ. of Tennessee Space Inst. (UTSI), Tullahoma, TN (United States)
  4. Univ. of California, San Diego, CA (United States)
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Cycling Cu2Sb films with fluoroethylene carbonate additive drastically improves the capacity retention of the electrode compared to cycling in pure PC with about 250 mAh g-1 retained capacity for about two hundred cycles. TEM photographs reveal that the pristine films are formed of nanoparticles of 5-20 nm diameters. XRD results highlight that during the first discharge the reaction leads to the formation of Na3Sb via an intermediate amorphous phase. During charge, Na3Sb crystallites convert into an amorphous phase, which eventually crystallizes into Cu2Sb at full charge, indicating a high degree of structural reversibility. The subsequent discharge is marked by a new plateau around 0.5 V at low Na/Sb content which does not correspond to the formation of a crystalline phase. XAS data show that the fully discharged electrode material has interatomic distances matching those expected for the coexistence of Cu and Na3Sb nanodomains. At 1 V charge, the structure somewhat differs from that of Cu2Sb whereas at 2 V charge, when all Na is removed, the structure is significantly closer to that of the starting material. 121Sb Mössbauer spectroscopy isomer shifts of Cu2Sb powder (-9.67 mm s-1) and thin films (-9.65 mm s-1) are reported for the first time, and agree with the value predicted theoretically. At full discharge, an isomer shift (-8.10 mm s-1) rather close to that of a Na3Sb reference powder (-8.00 mm s-1) is measured, in agreement with the formation of Na3Sb domains evidenced by XRD and XAS data. As a result, the isomer shift at 1 V charge (-9.29 mm s-1) is close to that of the pristine material and the higher value is in agreement with the lack of full desodiation at 1 V.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; DMR105717; AC02-98CH10886; FG02-05ER15688
OSTI ID:
1159405
Journal Information:
Journal of Physical Chemistry. C, Vol. 118, Issue 15; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 63 works
Citation information provided by
Web of Science

References (28)

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Cited By (12)

Synergistic effect of cross-linked carbon nanosheet frameworks and Sb on the enhancement of sodium storage performances journal January 2017
Alloy-Based Anode Materials toward Advanced Sodium-Ion Batteries journal June 2017
Superior Stable Self-Healing SnP 3 Anode for Sodium-Ion Batteries journal June 2015
In situ incorporation of nanostructured antimony in an N-doped carbon matrix for advanced sodium-ion batteries journal January 2019
Magnetron sputtering deposition of MSb(M=Fe, Ni, Co) thin films as negative electrodes for Li-ion and Na-ion batteries journal February 2019
Spherical nano-Sb@C composite as a high-rate and ultra-stable anode material for sodium-ion batteries journal September 2015
Low-Cost Metallic Anode Materials for High Performance Rechargeable Batteries journal July 2017
High-Performance Sb/Sb 2 O 3 Anode Materials Using a Polypyrrole Nanowire Network for Na-Ion Batteries journal March 2015
Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed γ-Valerolactone Production journal June 2015
Ultrafast and Highly Reversible Sodium Storage in Zinc-Antimony Intermetallic Nanomaterials journal December 2015
Carbon Anode Materials for Advanced Sodium-Ion Batteries journal March 2017
Sb-based electrode materials for rechargeable batteries journal January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copper antimony (Cu₂Sb) thin films
sodium-ion anode
transmission electron microscopy (TEM)
x-ray diffraction (XRD)
Cu and Sb K-edge x-ray absorption spectroscopy (XAS)
¹²¹Sb Mössbauer spectroscopy