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Title: Tris(trimethylsilyl) phosphite (TMSPi) and triethyl phosphite (TEPi) as electrolyte additives for lithium ion batteries: Mechanistic insights into differences during LiNi0.5Mn0.3Co0.2O2- Graphite full cell cycling

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.1101707jes· OSTI ID:1372387
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  1. Argonne National Lab. (ANL), Argonne, IL (United States)
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Here, tris(trimethylsilyl) phosphite (TMSPi) has emerged as an useful electrolyte additive for lithium ion cells. This work examines the use of TMSPi and a structurally analogous compound, triethyl phosphite (TEPi), in LiNi0.5Mn0.3Co0.2O2-graphite full cells, containing a (baseline) electrolyte with 1.2 M LiPF6 in EC: EMC (3:7 w/w) and operating between 3.0-4.4 V. Galvanostatic cycling data reveal a measurable difference in capacity fade between the TMSPi and TEPi cells. Furthermore, lower impedance rise is observed for the TMSPi cells, because of the formation of a P-and O-rich surface film on the positive electrode that was revealed by X-ray photoelectron spectroscopy data. Elemental analysis on negative electrodes harvested from cycled cells show lower contents of transition metal (TM) elements for the TMSPi cells than for the baseline and TEPi cells. Our findings indicate that removal of TMS groups from the central P-O core of the TMSPi additive enables formation of the oxide surface film. This film is able to block the generation of reactive TM-oxygen radical species, suppress hydrogen abstraction from the electrolyte solvent, and minimize oxidation reactions at the positive electrode-electrolyte interface. In contrast, oxidation of TEPi does not yield a protective positive electrode film, which results in inferior electrochemical performance.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1372387
Journal Information:
Journal of the Electrochemical Society, Vol. 164, Issue 7; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

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Cited By (4)

Scavenging Materials to Stabilize LiPF 6 ‐Containing Carbonate‐Based Electrolytes for Li‐Ion Batteries journal November 2018
Some Physical Properties of Ethylene Carbonate-Free Electrolytes journal January 2018
Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise journal January 2018
Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
25 ENERGY STORAGE
36 MATERIALS SCIENCE
electrolyte additive
high energy
high voltage
lithium-ion battery
oxide surface film
phosphite compound