AFM study of oxygen reduction products on HOPG in the LiPF6–DMSO electrolyte

Herrera, Santiago E.; Tesio, Alvaro Yamil; Clarenc, Romain; Calvo, Ernesto J.

doi:10.1039/c3cp54621g

Cited by 25 publications

(23 citation statements)

References 27 publications

(42 reference statements)

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“…31 The water content of the solvents was determined using the Karl Fisher 831 KF Coulometer (Metrohm) and resulted less than 30 ppm. The electrolyte solutions prepared in the glove box were transferred by syringes to the electrochemical cell without contact with the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

et al. 2015

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The O2/Li2O2 electrode reaction has been studied on low surface area Au electrodes in three solvent-electrolyte pairs (0.1 M LiPF6/DMSO, LiPF6/ACN, and LiBF4/ACN) using an electrochemical cell coupled to UHV XPS spectrometer, EQCM, AFM, and DEMS. The XPS spectra of the surfaces after treatment at selected electrode potentials for the O2 reduction and reoxidation of the surface show the presence of C and S from solvent decomposition and of F and P from electrolyte decomposition. Furthermore, Li 1s and O 1s peaks due to Li2O2 and decomposition products such as carbonate, organics, LiF, high oxidation sulfur, and phosphorus compounds were also observed. Using ACN instead of DMSO results in less solvent decomposition, whereas using LiBF4 results in less electrolyte decomposition. XPS, AFM, and EQCM show that O2 reduction products removal only takes place at very high overpotentials. In agreement with XPS which shows removal of carbonate surface species, DEMS confirms evolution of CO2 and consumption of O2 at 4.5 V, but LiF cannot be removed completely in a round trip of the Li-O2 battery cathode.

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Section: Introductionmentioning

confidence: 99%

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

et al. 2015

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“…20 On Au, due to the lack of step edges and a more uniform surface reactivity, Liu et al 21 concluded that a soluble LiO 2 species was initially formed that subsequently precipitates out on the surface as Li 2 O 2 . 22 S. E. Herrera et al 23 studied the formation of Li 2 O 2 in DMSO on HOPG using ex situ AFM, and herein an analogous AFM study in the Na-O 2 system of the growth and dissolution of NaO 2 precipitates on HOPG is presented.…”

mentioning

confidence: 99%

Growth and dissolution of NaO₂ in an ether-based electrolyte as the discharge product in the Na–O₂ cell

Aldous

Hardwick

2018

Chem. Commun.

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The deposition and dissolution of sodium superoxide (NaO) was investigated by atomic force microscopy. Rectangular prisms consisting of 8 smaller sub-structures grew from NaO platelets, when discharged in 0.5 M NaClO, diethylene glycol dimethyl ether on highly ordered pyrolytic graphite. During oxidation the 8 sub-structures are conserved. Ring-like structures of NaCO of 200 nm diameter remain at the end of oxidation.

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“…We have also investigated the morphology of oxygen reduction insoluble products in DMSO LiPF 6 electrolyte by ex situ AFM on HOPG after treatment at different electrode potentials for the oxygen reduction (discharge) and O 2 evolution by Li 2 O 2 oxidation (charge) . Decoration of step edges is apparent and also deposits at basal plane terraces grow by peroxide aggregation.…”

Section: Oxygen Reduction and Batteriesmentioning

confidence: 99%

The kinetics of oxygen electroreduction: A long way from iron rust to lithium-air batteries

Calvo

2014

Materials and Corrosion

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In this communication, we review the details of the oxygen electroreduction reaction on rust layers, passive iron and well defined iron oxides as cathodes for the reaction. In particular, we highlight the important electrocatalytic role of Fe(II) sites at the surface of the oxides in contact with the aqueous electrolyte. When the same reaction takes place at bifunctional cathodes with separated metal anodes which gives rise to metal-air batteries on which much attention has been paid recently in connection with electric vehicles. IntroductionIt seems most appropriate for the 60th birthday celebration of Professor Dr. Martin Stratmann to discuss some aspects of the oxygen reduction kinetics, a topic in which we share a common interest since our first meeting at CWRU in 1983. This is also a topic to which Martin Stratmann has made very substantial scientific contributions.The ubiquitous oxygen reduction reaction (ORR) [1] is very important in very different fields such as metal corrosion [2], fuel cells [3,4] and metal-air batteries [5], bio-fuel cells [6] and also the respiratory chain of biological cells [7]. Biology provides several mechanisms to activate the oxygen molecule such as through heme proteins, copper clusters and flavin containing proteins [8] while platinum based catalysts have been used for more than 50 years in fuel cell technology [9].The electrochemical reduction of oxygen involves up to four electrons and four protons transfer steps as shown in Scheme 1 to yield water with a number of adsorbed intermediates, so it is highly catalytic. A number of theories [11][12][13] and experimental [3,9,[14][15][16][17] approaches have been made to understand the role of oxygen reduction intermediates. In particular the role of H 2 O 2 has been investigated with the rotating ring disc electrode (RRDE) and mechanistic criteria were early developed [10].Since the start of the space race a great effort has been dedicated to fuel cells both in materials and electrocatalysis [9,18] particular the oxygen cathode with platinum and noble metal materials.

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AFM study of oxygen reduction products on HOPG in the LiPF6–DMSO electrolyte

Cited by 25 publications

References 27 publications

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

Growth and dissolution of NaO₂ in an ether-based electrolyte as the discharge product in the Na–O₂ cell

The kinetics of oxygen electroreduction: A long way from iron rust to lithium-air batteries

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AFM study of oxygen reduction products on HOPG in the LiPF6–DMSO electrolyte

Cited by 25 publications

References 27 publications

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

Growth and dissolution of NaO2 in an ether-based electrolyte as the discharge product in the Na–O2 cell

The kinetics of oxygen electroreduction: A long way from iron rust to lithium-air batteries

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Growth and dissolution of NaO₂ in an ether-based electrolyte as the discharge product in the Na–O₂ cell