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Title: The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface

Abstract

Electrochemical oxidation of carbonate esters at the LixNi0.5Mn1.5O4-δ/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of LixNi0.5Mn1.5O4-δ positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of MnII/III and NiII complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at LixNi0.5Mn1.5O4-δ, form a surface film that partially dissolves in the electrolyte. The dissolved MnIII complexes are reduced to their MnII analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li+ transport kinetics in Li-ion batteries.

Authors:
 [1];  [1];  [2];  [1];  [3];  [3];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Illinois, Chicago, IL (United States)
  3. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1210596
DOE Contract Number:  
SC0001294
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 10; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), defects, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Jarry, Angelique, Gottis, Sebastien, Yu, Young-Sang, Roque-Rosell, Josep, Kim, Chunjoong, Cabana, Jordi, Kerr, John B, and Kostecki, Robert. The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface. United States: N. p., 2015. Web. doi:10.1021/ja5116698.
Jarry, Angelique, Gottis, Sebastien, Yu, Young-Sang, Roque-Rosell, Josep, Kim, Chunjoong, Cabana, Jordi, Kerr, John B, & Kostecki, Robert. The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface. United States. https://doi.org/10.1021/ja5116698
Jarry, Angelique, Gottis, Sebastien, Yu, Young-Sang, Roque-Rosell, Josep, Kim, Chunjoong, Cabana, Jordi, Kerr, John B, and Kostecki, Robert. 2015. "The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface". United States. https://doi.org/10.1021/ja5116698.
@article{osti_1210596,
title = {The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface},
author = {Jarry, Angelique and Gottis, Sebastien and Yu, Young-Sang and Roque-Rosell, Josep and Kim, Chunjoong and Cabana, Jordi and Kerr, John B and Kostecki, Robert},
abstractNote = {Electrochemical oxidation of carbonate esters at the LixNi0.5Mn1.5O4-δ/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of LixNi0.5Mn1.5O4-δ positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of MnII/III and NiII complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at LixNi0.5Mn1.5O4-δ, form a surface film that partially dissolves in the electrolyte. The dissolved MnIII complexes are reduced to their MnII analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li+ transport kinetics in Li-ion batteries.},
doi = {10.1021/ja5116698},
url = {https://www.osti.gov/biblio/1210596}, journal = {Journal of the American Chemical Society},
number = 10,
volume = 137,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2015},
month = {Wed Mar 18 00:00:00 EDT 2015}
}

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