In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery

Qiao, Yu; Ye, Shen

doi:10.1021/acs.jpcc.5b03370

Cited by 121 publications

(214 citation statements)

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“…Replacing 18 O 2 with 16 O 2 was realized by 10 minute purging 16 O 2 through the Raman cell, during which the Au electrode potential was set to be 2.4 V. At the end of gas exchange, in situ SERS showed that Li 2 18 O 2 still dominates on Au as expected (Figure 2a,green curve). [22][23][24][25] Theintensity of the Li 2 16 O 2 band increases as af unction of discharging time,a nd one prominent feature is that prolonged discharging time (for example, > 5h)leads to the complete disappearance of the antecedently formed Li 2 18 O 2 and only Li 2 16 O 2 remains,i ndicating that the former has been replaced by the latter.T he displacement of Li 2 18 O 2 by Li 2 16 O 2 detected by surface-sensitive SERS technique suggests that the reactive sites of ORR are at the Au j Li 2 O 2 interface,which in return provides evidence that at the stage of sudden death ORR is limited by the electron transport instead of Li + and O 2 transport. After 1hdischarging at 2.0 V, aweak band at about 790 cm À1 ascribed to the formation of Li 2 16 O 2 was observed (Figure 2a, blue curve).…”

Section: Angewandte Chemiementioning

confidence: 90%

“…Avery recent in situ TEM work on the Li-O 2 battery containing liquid electrolyte by Kushima et al [20] showed that the discharging reaction occurred at the interface between electrolyte and the reaction product, whereas in charging,t he reactant was decomposed at the contact with the cathode,i ndicating that the Li + ion diffusivity/electronic conductivity is the limiting factor in discharging/charging,r espectively.H owever,t he above in situ SEM and TEM studies are conducted under electron beam radiation (potentially damaging Li 2 O 2 and inducing defects or parasitic reactions) and high charging potentials (> 6o r even 8V) [18,19] are applied to decompose Li 2 O 2 ,w hich are very different to the situation of typical Li-O 2 cells containing liquid electrolytes. [23][24][25] It has been reported that discharging current density plays ac ritical role in the formation of Li 2 O 2 ,t hat is,s olution/ surface formation of Li 2 O 2 can be achieved by low/high current densities. 3.8 nm) by discharging to the state of sudden death.…”

Section: Identifying Reactivesites and Transport Limitations Of Oxygementioning

confidence: 99%

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Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death

et al. 2016

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Discharging of the aprotic Li-O2 battery relies on the O2 reduction reaction (ORR) forming solid Li2 O2 in the positive electrode, which is often characterized by a sharp voltage drop (that is, sudden death) at the end of discharge, delivering a capacity far below its theoretical promise. Toward unlocking the energy capabilities of Li-O2 batteries, it is crucial to have a fundamental understanding of the origin of sudden death in terms of reactive sites and transport limitations. Herein, a mechanistic study is presented on a model system of Au|Li2 O2 |Li(+) electrolyte, in which the Au electrode was passivated with a thin Li2 O2 film by discharging to the state of sudden death. Direct conductivity measurement of the Li2 O2 film and in situ spectroscopic study of ORR using (18) O2 for passivation and (16) O2 for further discharging provide compelling evidence that ORR (and O2 evolution reaction as well) occurs at the buried interface of Au|Li2 O2 and is limited by electron instead of Li(+) and O2 transport.

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Section: Angewandte Chemiementioning

confidence: 90%

Section: Identifying Reactivesites and Transport Limitations Of Oxygementioning

confidence: 99%

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death

et al. 2016

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“…This interpretation is also in good agreement with the results presented by Yu and Ye who have shown by means of UV/vis spectroscopy that parallel to peroxide also a significant amount of superoxide is formed and that the share increases as the electrode is deactivated. 37 RRDE-measurements in connection with potential step experiments also show that ring currents are observed irrespective to which potential the disc electrode is stepped, whereas the peak height of the ring current depends on the disc potential. 11 It is the prevailing view in literature that the species that reacts at the ring electrode is superoxide.…”

mentioning

confidence: 82%

“…Recently, based on UV/vis and SERS studies, Yu and Ye have proposed that the second peak is due to the oxidation of LiO 2 . 37 This reaction should come along with a z-value of only one. Based on the data presented in Figure 8B we have to reject this interpretation.…”

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confidence: 99%

A Comprehensive Study on Oxygen Reduction and Evolution from Lithium Containing DMSO Based Electrolytes at Gold Electrodes

Bondue

Hegemann

Molls

et al. 2016

J. Electrochem. Soc.

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In the present study, we investigated the reduction and the evolution of oxygen from lithium containing DMSO based electrolytes at gold. The number of electrons that are transferred per O 2 (z-value) during oxygen reduction depends on the structure of the electrode: Despite the presence of Li + , O 2 is reduced electrochemically to superoxide at smooth gold electrodes and at low overpotentials. At porous electrodes a z-value close to 2 e − /O 2 indicates Li 2 O 2 -formation even at low overpotentials. This is ascribed to a reaction of superoxide, which is catalyzed by gold-particles at open circuit. This behavior is also responsible for the non-proportionality between reduced and evolved amounts of oxygen. Furthermore, we observed a linear relationship between evolved amounts of CO 2 and reduced amounts of oxygen, indicative for electrolyte decomposition during oxygen reduction. Combined electrochemical quartz crystal microbalance (eQCMB) and Differential electrochemical mass spectroscopy (DEMS) measurements reveal that mass changes that occur in the anodic sweep are due to the evolution of CO 2 , whereas oxygen evolution takes place without any mass changes. The observed m.p.e-values (mass changes per transferred electron) are affected by convection due to the formation of soluble reduction products which observed in rotating ring disc electrode measurements. It is common knowledge that, in order to electrify automotive traffic, portable storage systems for electrical energy are required. For the time being lithium-ion-batteries are the most promising candidates for a real life technical application. However, due to the requirement of heavy metal oxides as cathode material their theoretical specific energy density is too low to replace current fuels.1 Due to the low weight and very negative standard potential of lithium, a lithiumoxygen battery has, in theory, a specific energy density of 13.8 kJ/g (considering the weight of the discharged state and the formation of Li 2 O 2 rather than Li 2 O) and a theoretical electrochemical efficiency of 90.2% as can easily be calculated from thermodynamics 2,3 (10% of the energy is lost due to the heat flow caused by the entropy).It is in general accepted that reduction of oxygen in Li + -containing organic solvents yields Li 2 O 2 as a reaction product. [4][5][6] The process of Li 2 O 2 formation in DMSO seems to be unique as it involves the formation of a superoxide intermediate. [7][8][9][10][11] This has not only been shown by CV and rotating ring disc electrode (RRDE) measurements but also by combining electrochemistry with spin-trap experiments and EPRspectroscopy 12 as well as by DEMS experiments. 7 The remarkable stability of superoxide, despite the presence of Li + -cations, was ascribed to the large donor number of DMSO 8,13 of nearly 125 kJ/mol 14 as compared to acetonitrile with a donor number of 58.9 kJ/mol. 14 In the latter solvent superoxide intermediates have not been reported so far. However, whether Li 2 O 2 forms via lithium induced disproportionation of...

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“…In thef ramework of Pearson's hard-soft acid-base (HSAB) theory,t his effect can be explained by increased stability of the solvation shell around the Li + ions in high DN solvents. [10] ) This concept was further developedb yJ ohnson, [9] who reported that the Li + -solventi nteraction was considered as the main factor determining LiO 2 solubility.I tw as concludedt hat in high DN solvents, disproportionation of LiO 2 in solutiond ominated over surfacee lectrochemical processes.…”

Section: Introductionmentioning

confidence: 99%

Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium–Oxygen Battery Electrolytes

Смирнов

Kislenko

2017

ChemPhysChem

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The molecular life of intermediates, namely, O and Li , produced during the discharge of aprotic Li-O batteries was investigated by molecular dynamics simulation. This work is of potential interest in the development of new electrolytes for Li-air batteries. We present the results on the structure and stability of the Li and O solvation shells and the thermodynamics and kinetics of the ion-association reaction in solvents such as dimethyl sulfoxide (DMSO), dimethoxyethane (DME), and acetonitrile (ACN). The residence time of solvent molecules in the Li solvation shell increases with the solvent donor number and is 100 times larger in DMSO than in ACN. In DMSO and DME, the Li ion diffuses with its solvation shell as a whole. On the contrary, in ACN it diffuses as a "bare" ion because of weak solvation. The rate constant for the association of the lithium ion with the superoxide anion in DMSO is two orders of magnitude slower than that in ACN due to fact that the free-energy barrier is 2.5 times larger in DMSO than in ACN. In addition, we show that despite the strong dependence of the Li shell stability on donor number, the rate of association does not necessarily correlate with this solvent property.

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In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery

Cited by 121 publications

References 37 publications

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death

A Comprehensive Study on Oxygen Reduction and Evolution from Lithium Containing DMSO Based Electrolytes at Gold Electrodes

Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium–Oxygen Battery Electrolytes

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In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery

Cited by 121 publications

References 37 publications

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O2 Batteries at the Stage of Sudden Death

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O2 Batteries at the Stage of Sudden Death

A Comprehensive Study on Oxygen Reduction and Evolution from Lithium Containing DMSO Based Electrolytes at Gold Electrodes

Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium–Oxygen Battery Electrolytes

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Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O₂ Batteries at the Stage of Sudden Death