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Title: Elucidating the Irreversible Mechanism and Voltage Hysteresis in Conversion Reaction for High-Energy Sodium-Metal Sulfide Batteries

Journal Article · · Advanced Energy Materials
 [1];  [1];  [1];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
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We present that irreversible electrochemical behavior and large voltage hysteresis are commonly observed in battery materials, in particular for materials reacting through conversion reaction, resulting in undesirable round-trip energy loss and low coulombic efficiency. Seeking solutions to these challenges relies on the understanding of the underlying mechanism and physical origins. Here, this study combines in operando 2D transmission X-ray microscopy with X-ray absorption near edge structure, 3D tomography, and galvanostatic intermittent titration techniques to uncover the conversion reaction in sodium–metal sulfide batteries, a promising high-energy battery system. This study shows a high irreversible electrochemistry process predominately occurs at first cycle, which can be largely linked to Na ion trapping during the first desodiation process and large interfacial ion mobility resistance. Subsequently, phase transformation evolution and electrochemical reaction show good reversibility at multiple discharge/charge cycles due to materials' microstructural change and equilibrium. The origin of large hysteresis between discharge and charge is investigated and it can be attributed to multiple factors including ion mobility resistance at the two-phase interface, intrinsic slow sodium ion diffusion kinetics, and irreversibility as well as ohmic voltage drop and overpotential. In conclusion, this study expects that such understandings will help pave the way for engineering design and optimization of materials microstructure for future-generation batteries.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; AC02-98CH10886; AC02-06CH11357; DE‐AC02‐98CH10886
OSTI ID:
1392215
Alternate ID(s):
OSTI ID: 1401282
Report Number(s):
BNL-114149-2017-JA
Journal Information:
Advanced Energy Materials, Vol. 7, Issue 14; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 66 works
Citation information provided by
Web of Science

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Cited By (6)

General Synthesis of Dual Carbon-Confined Metal Sulfides Quantum Dots Toward High-Performance Anodes for Sodium-Ion Batteries journal August 2017
Enabling Full Conversion Reaction with High Reversibility to Approach Theoretical Capacity for Sodium Storage journal September 2019
Promoting Highly Reversible Sodium Storage of Iron Sulfide Hollow Polyhedrons via Cobalt Incorporation and Graphene Wrapping journal July 2019
One-Step In Situ Synthesis of Three-Dimensional NiSb Thin Films as Anode Electrode Material for the Advanced Sodium-Ion Battery: One-Step In Situ Synthesis of Three-Dimensional NiSb Thin Films as Anode Electrode Material for the Advanced Sodium-Ion Battery journal February 2018
The State and Challenges of Anode Materials Based on Conversion Reactions for Sodium Storage journal March 2018
Self-limiting electrode with double-carbon layers as walls for efficient sodium storage performance journal January 2019

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Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
batteries
synchrotron
conversion reaction
electrochemistry