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DOI	10.1039/c9ee01453e
	Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries
	Mourad E.; Petit Y.K.; Spezia R.; Samojlov A.; Summa F.F.; Prehal C.; Leypold C.; Mahne N.; Slugovc C.; Fontaine O.; Brutti S.; Freunberger S.A.
发表日期	2019
ISSN	17545692
起始页码	2559
结束页码	2568
卷号	12 期号:8
英文摘要	Aprotic alkali metal-oxygen batteries require reversible formation of metal superoxide or peroxide on cycling. Severe parasitic reactions cause poor rechargeability, efficiency, and cycle life and have been shown to be caused by singlet oxygen (1O2) that forms at all stages of cycling. However, its formation mechanism remains unclear. We show that disproportionation of superoxide, the product or intermediate on discharge and charge, to peroxide and oxygen is responsible for 1O2 formation. While the overall reaction is driven by the stability of peroxide and thus favored by stronger Lewis acidic cations such as Li+, the 1O2 fraction is enhanced by weak Lewis acids such as organic cations. Concurrently, the metal peroxide yield drops with increasing 1O2. The results explain a major parasitic pathway during cell cycling and the growing severity in K-, Na-, and Li-O2 cells based on the growing propensity for disproportionation. High capacities and rates with peroxides are now realized to require solution processes, which form peroxide or release O2via disproportionation. The results therefore establish the central dilemma that disproportionation is required for high capacity but also responsible for irreversible reactions. Highly reversible cell operation requires hence finding reaction routes that avoid disproportionation. © The Royal Society of Chemistry 2019.
英文关键词	Lithium compounds; Metals; Oxidation; Peroxides; Positive ions; Sodium compounds; Disproportionations; Formation mechanism; Irreversible reactions; Organic cations; Overall reactions; Parasitic reaction; Reversible formation; Solution process; Secondary batteries; cation; chemical reaction; energy efficiency; formation mechanism; fuel cell; metal; oxygen
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/189850
作者单位	Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, Graz, 8010, Austria; Laboratoire de Chimie Théorique, UMR 7616 CNRS, Sorbonne Université, CC 137, 4, Place Jussieu, Paris Cedex 05, 75252, France; Dipartimento di Scienze, Università della Basilicata, V.le Ateneo Lucano 10, Potenza, 85100, Italy; Institut Charles Gerhardt Montpellier, UMR 5253, CC 1701, Université Montpellier, Place Eugène Bataillon, Montpellier Cedex 5, 34095, France; Réseau sur le Stockage Electrochimique de l'Energie (RS2E), CNRS FR3459, 33 rue Saint Leu, Amiens, 80039, France; Dipartimento di Chimica, Università di Roma la Sapienza, P.le A. Moro 5, Roma, 00185, Italy
推荐引用方式 GB/T 7714	Mourad E.,Petit Y.K.,Spezia R.,et al. Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries[J],2019,12(8).
APA	Mourad E..,Petit Y.K..,Spezia R..,Samojlov A..,Summa F.F..,...&Freunberger S.A..(2019).Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries.Energy & Environmental Science,12(8).
MLA	Mourad E.,et al."Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries".Energy & Environmental Science 12.8(2019).