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Title: Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives

Abstract

A new class of electrolyte additives based on cyclic fluorinated phosphate esters was rationally designed and identified as being able to stabilize the surface of a LiNi0.5Mn0.3Co0.2O2 (NMC532) cathode when cycled at potentials higher than 4.6 V vs Li+/Li. Cyclic fluorinated phosphates were designed to incorporate functionalities of various existing additives to maximize their utilization. The synthesis and characterization of these new additives are described and their electrochemical performance in a NMC532/graphite cell cycled between 4.6 and 3.0 V are investigated. With 1.0 wt % 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (TFEOP) in the conventional electrolyte the NMC532/graphite cell exhibited much improved capacity retention compared to that without any additive. The additive is believed to form a passivation layer on the surface of the cathode via a sacrificial polymerization reaction as evidenced by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonsance (NMR) analysis results. The rational pathway of a cathode-electrolyte-interface formation was proposed for this type of additive. Both experimental results and the mechanism hypothesis suggest the effectiveness of the additive stems from both the polymerizable cyclic ring and the electron-withdrawing fluorinated alkyl group in the phosphate molecular structure. The successful development of cyclic fluorinated phosphate additives demonstrated that this new functionality selection principle,more » by incorporating useful functionalities of various additives into one molecule, is an effective approach for the development of new additives.« less

Authors:
ORCiD logo;  [1]; ORCiD logo; ORCiD logo; ; ; ; ;  [1];
  1. Department of Mechanical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, Massachusetts 01609, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1393464
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 36; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
fluorinated cyclic phosphate, electrolyte additive, functionality selection principle, high voltage electrolyte, post-test analysis, LiNi0.5Mn0.3Co0.2O2 cathode

Citation Formats

Su, Chi-Cheung, He, Meinan, Peebles, Cameron, Zeng, Li, Tornheim, Adam, Liao, Chen, Zhang, Lu, Wang, Jie, Wang, Yan, and Zhang, Zhengcheng. Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives. United States: N. p., 2017. Web. doi:10.1021/acsami.7b08953.
Su, Chi-Cheung, He, Meinan, Peebles, Cameron, Zeng, Li, Tornheim, Adam, Liao, Chen, Zhang, Lu, Wang, Jie, Wang, Yan, & Zhang, Zhengcheng. Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives. United States. doi:10.1021/acsami.7b08953.
Su, Chi-Cheung, He, Meinan, Peebles, Cameron, Zeng, Li, Tornheim, Adam, Liao, Chen, Zhang, Lu, Wang, Jie, Wang, Yan, and Zhang, Zhengcheng. Wed . "Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives". United States. doi:10.1021/acsami.7b08953.
@article{osti_1393464,
title = {Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives},
author = {Su, Chi-Cheung and He, Meinan and Peebles, Cameron and Zeng, Li and Tornheim, Adam and Liao, Chen and Zhang, Lu and Wang, Jie and Wang, Yan and Zhang, Zhengcheng},
abstractNote = {A new class of electrolyte additives based on cyclic fluorinated phosphate esters was rationally designed and identified as being able to stabilize the surface of a LiNi0.5Mn0.3Co0.2O2 (NMC532) cathode when cycled at potentials higher than 4.6 V vs Li+/Li. Cyclic fluorinated phosphates were designed to incorporate functionalities of various existing additives to maximize their utilization. The synthesis and characterization of these new additives are described and their electrochemical performance in a NMC532/graphite cell cycled between 4.6 and 3.0 V are investigated. With 1.0 wt % 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (TFEOP) in the conventional electrolyte the NMC532/graphite cell exhibited much improved capacity retention compared to that without any additive. The additive is believed to form a passivation layer on the surface of the cathode via a sacrificial polymerization reaction as evidenced by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonsance (NMR) analysis results. The rational pathway of a cathode-electrolyte-interface formation was proposed for this type of additive. Both experimental results and the mechanism hypothesis suggest the effectiveness of the additive stems from both the polymerizable cyclic ring and the electron-withdrawing fluorinated alkyl group in the phosphate molecular structure. The successful development of cyclic fluorinated phosphate additives demonstrated that this new functionality selection principle, by incorporating useful functionalities of various additives into one molecule, is an effective approach for the development of new additives.},
doi = {10.1021/acsami.7b08953},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 36,
volume = 9,
place = {United States},
year = {2017},
month = {8}
}