Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds

Tornheim, Adam; Garcia, Juan C.; Sahore, Ritu; Iddir, Hakim; Bloom, Ira; Zhang, Zhengcheng

doi:10.1149/2.0951902jes

Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds

Journal Article · Thu Feb 07 00:00:00 EST 2019 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0951902jes· OSTI ID:1494582

^[1]; ^[1]; Sahore, Ritu ^[1]; Iddir, Hakim ^[1]; Bloom, Ira ^[1]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)

In this work, multiple phosphorus-containing compounds were evaluated as electrolyte additives for their reactivity at the cathode surface using LiNi_0.5Mn_0.3Co_0.2O₂ (NMC532) // Li₄Ti₅O₁₂ (LTO) cells with both cycling and high voltage potentiostatic holds. Additives surveyed include phosphite and phosphate derivatives with either trifluoroethyl, ethyl, or trimethylsilyl groups. With the same substituents, phosphite additives showed lower Coulombic efficiency (CE) and higher oxidation current during the potentiostatic hold. Regardless of substitution group, all phosphates showed slightly higher CE than the additive-free electrolyte (baseline), although no additive significantly decreases oxidation reactions over the course of the potentiostatic hold. Post-mortem X-ray photoelectron spectroscopy analysis of the cathodes indicates that the additive with trimethylsilyl group leads to significantly higher incidence of oxygen and phosphorus on the cathode surface for both phosphites and phosphates. Atomistic simulations indicate the susceptibility of these additives to electrochemical and chemical oxidation, showing chemical oxidation to be much more likely with the phosphite additives. Lastly, the identity of the ligands on the phosphorus-containing additive can dramatically affect both the decomposition current as well as cathode surface after the potentiostatic hold.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1494582

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 4 Vol. 166; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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