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Title: Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds

Abstract

Surface degradation of lithium-ion cathodes at high voltages represents a significant barrier to increasing the useable energy of conventional cathodes. Though much work has been focused on mitigating the detrimental effects of such phenomena, the complex and correlated mechanisms involved have made progress difficult. Herein, the effect of electrolyte identity on surface degradation is examined. LiNi0.5Mn0.3Co0.2O2 (NMC532)/Li4Ti5O12 (LTO) full cells were constructed using three different electrolytes: a baseline organic carbonate electrolyte, a baseline organic carbonate electrolyte with an oxidizable additive, and a fluorinated carbonate electrolyte. Each system was subjected to a 60 h potentiostatic hold at 3.05 V (4.6 V vs. Li+/Li) and subsequently deconstructed for characterization via transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Molecular simulations were carried out on each distinct component of the three electrolytes in contact with crystal surfaces of an NMC532 particle. Results indicate an affinity for the additive-containing electrolyte to extract atomic oxygen from the cathode surface, whereas the fluorinated electrolyte components have negligible interactions. Hydrogen abstraction from the baseline electrolyte is facilitated by the NMC532 surface. TEM analysis of cathode surfaces, after the potentiostatic holds, revealed that the NMC532 particles cycled with the additive-containing electrolyte underwent significant surface degradation, includingmore » changes to local crystal structure in a region penetrating 20-40 nm from the surface; consistent with oxygen and lithium loss from the cathode material. However, the NMC532 in contact with the fluorinated electrolyte showed a disordered layer of just a few nm in thickness, similar to the depth of crystal disorder observed in pristine NMC532 primary particles. EELS data of the oxygen K-edge also indicated transition metal (TM) reduction, consistent with oxygen loss and changes in crystal structure extending into the cathode surface for each of the electrolytes surveyed. These surface reactions, including oxygen loss, are shown to correlate well with elevated oxidation currents and surface reconstructions of cathode particles.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technologies (VTO); National Science Foundation (NSF)
OSTI Identifier:
1567741
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 55
Country of Publication:
United States
Language:
English
Subject:
cathode/electrolyte interface; electrolytes; high voltages; lithium-ion batteries

Citation Formats

Tornheim, Adam, Sharifi-Asl, Soroosh, Garcia, Juan C., Bareño, Javier, Iddir, Hakim, Shahbazian-Yassar, Reza, and Zhang, Zhengcheng. Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds. United States: N. p., 2019. Web. doi:10.1016/j.nanoen.2018.10.065.
Tornheim, Adam, Sharifi-Asl, Soroosh, Garcia, Juan C., Bareño, Javier, Iddir, Hakim, Shahbazian-Yassar, Reza, & Zhang, Zhengcheng. Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds. United States. doi:10.1016/j.nanoen.2018.10.065.
Tornheim, Adam, Sharifi-Asl, Soroosh, Garcia, Juan C., Bareño, Javier, Iddir, Hakim, Shahbazian-Yassar, Reza, and Zhang, Zhengcheng. Tue . "Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds". United States. doi:10.1016/j.nanoen.2018.10.065.
@article{osti_1567741,
title = {Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds},
author = {Tornheim, Adam and Sharifi-Asl, Soroosh and Garcia, Juan C. and Bareño, Javier and Iddir, Hakim and Shahbazian-Yassar, Reza and Zhang, Zhengcheng},
abstractNote = {Surface degradation of lithium-ion cathodes at high voltages represents a significant barrier to increasing the useable energy of conventional cathodes. Though much work has been focused on mitigating the detrimental effects of such phenomena, the complex and correlated mechanisms involved have made progress difficult. Herein, the effect of electrolyte identity on surface degradation is examined. LiNi0.5Mn0.3Co0.2O2 (NMC532)/Li4Ti5O12 (LTO) full cells were constructed using three different electrolytes: a baseline organic carbonate electrolyte, a baseline organic carbonate electrolyte with an oxidizable additive, and a fluorinated carbonate electrolyte. Each system was subjected to a 60 h potentiostatic hold at 3.05 V (4.6 V vs. Li+/Li) and subsequently deconstructed for characterization via transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Molecular simulations were carried out on each distinct component of the three electrolytes in contact with crystal surfaces of an NMC532 particle. Results indicate an affinity for the additive-containing electrolyte to extract atomic oxygen from the cathode surface, whereas the fluorinated electrolyte components have negligible interactions. Hydrogen abstraction from the baseline electrolyte is facilitated by the NMC532 surface. TEM analysis of cathode surfaces, after the potentiostatic holds, revealed that the NMC532 particles cycled with the additive-containing electrolyte underwent significant surface degradation, including changes to local crystal structure in a region penetrating 20-40 nm from the surface; consistent with oxygen and lithium loss from the cathode material. However, the NMC532 in contact with the fluorinated electrolyte showed a disordered layer of just a few nm in thickness, similar to the depth of crystal disorder observed in pristine NMC532 primary particles. EELS data of the oxygen K-edge also indicated transition metal (TM) reduction, consistent with oxygen loss and changes in crystal structure extending into the cathode surface for each of the electrolytes surveyed. These surface reactions, including oxygen loss, are shown to correlate well with elevated oxidation currents and surface reconstructions of cathode particles.},
doi = {10.1016/j.nanoen.2018.10.065},
journal = {Nano Energy},
number = ,
volume = 55,
place = {United States},
year = {2019},
month = {1}
}