Manganese sequestration and improved high-temperature cycling of Li-ion batteries by polymeric aza-15-crown-5

Mn cation trapping by polymeric aza-15-crown-5 ethers is an effective means for mitigating the consequences of Mn dissolution in Li-ion batteries. Mn cations trapping was investigated in lithium manganese oxide (LMO) spinel-graphite (GR) cells containing 1 M LiPF sub(6) in ethylene carbonate (EC):di...

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Bibliographic Details
Published in:Journal of power sources 2014-12, Vol.272, p.1134-1141
Main Authors: ZICHENG LI, PAURIC, Allen D, GOWARD, Gillian R, FULLER, Timothy J, ZIEGELBAUER, Joseph M, BALOGH, Michael P, HALALAY, Ion C
Format: Article
Language:English
Subjects:
Applied sciences
Cations
Cycles
Direct energy conversion and energy accumulation
Electrical engineering. Electrical power engineering
Electrical power engineering
Electrochemical conversion: primary and secondary batteries, fuel cells
Electrodes
Exact sciences and technology
Lithium-ion batteries
Manganese
Reduction
Separators
Trapping
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Summary:Mn cation trapping by polymeric aza-15-crown-5 ethers is an effective means for mitigating the consequences of Mn dissolution in Li-ion batteries. Mn cations trapping was investigated in lithium manganese oxide (LMO) spinel-graphite (GR) cells containing 1 M LiPF sub(6) in ethylene carbonate (EC):diethyl carbonate (DEC) 1:2 v/v. A commercial polyolefin separator membrane coated with poly[divinylbenzene-(vinylbenzyl-aza-15-crown-5)-vinylbenzylchlori d e)] effected a 39% reduction in capacity loss rate during cycling at 50 [degrees]C with 100% depth of discharge (DOD) at C/5 rate. Simultaneously, a 50-60% reduction in the Mn deposited at the negative electrode, and a 6x to 10x increase in the Mn on the coated separator were observed for cells with coated separators, over baseline cells with plain separators. X-ray absorption near-edge spectroscopy (XANES) yielded average oxidation states near +3 for Mn cations in graphite electrodes and separators from cycled cells, suggesting that Mn metal or in oxidation state +2 can only be minor fractions of the Mn existing outside the positive electrode. We discuss the implications of these results for choosing an optimal chelating agent. We also show that the cation chelating polymer reported here is compatible with existing manufacturing processes for Li-ion battery separators.
ISSN:0378-7753
1873-2755
DOI:10.1016/j.jpowsour.2014.04.073