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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja5116698· OSTI ID:1210596
 [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)
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC); Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE SC Office of Basic Energy Sciences (SC-22)
DOE Contract Number:
SC0001294
OSTI ID:
1210596
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 137
Country of Publication:
United States
Language:
English

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Related Subjects

energy storage (including batteries and capacitors)
defects
charge transport
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synthesis (novel materials)