The kinetics of the oxygen—peroxide couple on carbon

Yeager, Ernest; Krouse, Philip; Rao, K. V. S. Rama

doi:10.1016/0013-4686(64)80075-x

Cited by 85 publications

(75 citation statements)

References 6 publications

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“…However, at the optimum values of the parameters for model D, the partial current due to reaction [30] is on the average less than 2% of the total current over the entire range of the applied potential. This observation supports the contention of Yeager et al (28) that the contribution of reaction [30] to the overall current over the potential range considered is negligible. Therefore, model E can conveniently be chosen to describe the data.…”

Section: Evaluation Of Electrochemical Parameters From Polarization Dsupporting

confidence: 91%

“…The results presented here confirm the claim of Brezina et al (39) that the reduction of O2 on Ag electrode involves the parallel mechanism. The results presented here also indicate that the final reduction product observed at the limiting current of the first wave is due predominantly to reaction [28], the direct 4e-process, and that observed at the second wave is due mainly to reaction [30], the peroxide process. The depression in the polarization curve can be attributed to the competition between reactions [28] and [29] for O2 species at the electrode surface (see Ref.…”

Section: Evaluation Of Electrochemical Parameters From Polarization Dsupporting

confidence: 65%

“…[28] to [31], respectively. The kinetic model for oxygen reduction chosen for a priori sensitivity analysis was kinetic model A, the comprehensive model for oxygen reduction.…”

Section: Resultsmentioning

confidence: 99%

“…--The first reaction system analyzed with the parameter estimation code was the data of Yeager et al (28) for the cathodic reduction of oxygen on pyrolytic carbon electrode. The disk area of the electrode was given as 0.18 cm 2, and the solution concentration was 4.0M with respect to OHand 0.016M with respect to HO2-at 25~ The partial pressure of oxygen was 0.97 atmosphere.…”

Section: Evaluation Of Electrochemical Parameters From Polarization Dmentioning

confidence: 99%

“…The disk area of the electrode was given as 0.18 cm 2, and the solution concentration was 4.0M with respect to OHand 0.016M with respect to HO2-at 25~ The partial pressure of oxygen was 0.97 atmosphere. The model proposed by Yeager and his group (28) for this system was model E in Table I, the reduction of 02 to peroxide stage only.…”

Section: Evaluation Of Electrochemical Parameters From Polarization Dmentioning

confidence: 99%

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Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

Adanuvor

White

1988

J. Electrochem. Soc.

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An alternative approach to classical methods of electrochemical data analysis is presented. This alternative method is based on nonlinear parameter estimation and model discrimination techniques. The method is used to obtain the relevant kineuc ana transport parameters and to elucidate the kinetic mechanism of 02 reduction at carbon and silver electrodes in alkaline electrolytes.Conventional methods for electrochemical data analysis generally tend to focus on a narrow range of the kinetic expressions describing the electrochemical process, such as the Tafel or the linear segments of typical polarization curves. Focus on these sections of the polarization curves produces a set of parameter values which electrochemists have traditionally used to elucidate the mechanisms of electrochemical reactions. However, in most instances, the linear and Tafel segments of these curves are distorted by diffusion processes, the reverse reaction in the neighborhood of the equilibrium potential, and coupling effects of other reactions. Therefore, parameters estimated from the Tafel or linear regions of the polarization curves, especially for complex electrode reaction systems, may not reflect the true values of the parameters of the electrode reactions under consideration. For instance, where the electrode reaction is relatively fast, the Tafel segment may be so short as to create difficulty in accurately estimating the parameters. On the other hand, for slow electrode reactions, the polarization curves can have several Tafel segments with transition regions, where the reaction from one segment could be coupled with that in another segment. McIntyre (1) noted the coupling effect of a regenerative process of a heterogeneous catalytic electrode reaction over the complete potential range in which the electroactive species was reduced and recommended that the coupling effect be taken into account if kinetic parameters characteristic of the charge-transfer reaction are to be obtained. On the other hand, the linear region extends only a few millivolts beyond the equilibrium or open-circuit potential. As pointed out by Nagy et al. (2), measurements at such low overpotentials are often hampered by signal-to-noise ratio problems, and extrapolation from the linear to higher overpotential range as commonly done in electrochemical studies is generally questionable.Most kinetic models, in addition to relating the overall process and the component steps to the potential driving force and to the concentrations of reactants, products, and * Electrochemical Society Active Member.intermediates, must also take into account the transport O f reacting species, intermediates, and products to and from the electrode surface. Furthermore, consideration of homogeneous reactions in the solution and heterogeneous non-charge transfer reactions at the electrode surface increases the complexity of the system of model equations needed to evaluate the kinetic parameters. This system of model equations is normally described by a set of differential equatio...

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Section: Evaluation Of Electrochemical Parameters From Polarization Dsupporting

confidence: 91%

Section: Evaluation Of Electrochemical Parameters From Polarization Dsupporting

confidence: 65%

“…[28] to [31], respectively. The kinetic model for oxygen reduction chosen for a priori sensitivity analysis was kinetic model A, the comprehensive model for oxygen reduction.…”

Section: Resultsmentioning

confidence: 99%

Section: Evaluation Of Electrochemical Parameters From Polarization Dmentioning

confidence: 99%

Section: Evaluation Of Electrochemical Parameters From Polarization Dmentioning

confidence: 99%

See 3 more Smart Citations

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

Adanuvor

White

1988

J. Electrochem. Soc.

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Electrochemistry at Highly Oriented Pyrolytic Graphite (HOPG): Toward a New Perspective

Güell¹,

Tan²,

Unwin³

et al. 2015

Advances in Electrochemical Sciences and Engineering

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Recent Progress in Developing a LiOH‐Based Reversible Nonaqueous Lithium–Air Battery

et al. 2022

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By replacing the conventional graphite-based anode (372 mAh g −1 for LiC 6 , on the basis of mass of C) with silicon (3579 mAh g −1 for Li 15 Si 4 , on the basis of mass of Si) or lithium metal (3860 mAh g −1 ; based on the mass of Li) anodes, the practical energy density of LIB single cells can be increased to 300-400 Wh kg −1 . [4] Nevertheless, to surpass the commonly targeted goal of 500 Wh kg −1 , [5] alternative cathodic chemistries beyond Li-ion intercalation are required. Using O 2 as an active material for electrochemical energy storage is appealing in terms of cost and availability, and when coupled to Li metal, lithium-air batteries (LABs) could deliver energy densities up to 3505 Wh kg −1 (theoretical value). [1c,6] Several studies have demonstrated nonaqueous Li-O 2 batteries with energy densities of up to 1230 Wh kg −1 using novel cell designs, [7] although the cycle life needs to be improved. Table S1, Supporting Information, summarizes the high-energy lithium-air full cells reported to date.The theoretical energy density of nonaqueous LABs depends on the specific cathodic half-cell reaction (Equations ( 1)-( 4), note that all voltages are referred to against Li/Li + ), and thus the chemical composition of the discharge product. [8] Thus far, successfully tested discharge products for aprotic LABs include LiO 2 , Li 2 O 2 , Li 2 O, and LiOH. Both Li 2 O 2 and Li 2 O are thermodynamically stable compounds (Equations ( 1) and ( 2)), whereas LiO 2 is unstable at standard conditions but has been reported to form in LABs assisted by Ir-and Pd-catalytic systems (Equation ( 3)). [8a-d] Formation of Li 2 O during discharge involves rupture of the OO bond and is thus less kinetically favorable than Li 2 O 2 formation, unless discharge occurs in the presence of a catalyst such as nickel at above 150 °C. 2 2 1 8b,9 (4) Notably, one issue that LiO 2 , Li 2 O 2 , and Li 2 O have in common is their moisture and carbon dioxide sensitivity, as The realization of practical nonaqueous lithium-air batteries (LABs) calls for novel strategies to address their numerous theoretical and technical challenges. LiOH formation/decomposition has recently been proposed as a promising alternative route to cycling LABs via Li 2 O 2 . Herein, the progress in developing LiOH-based nonaqueous LABs is reviewed. Various catalytic systems, either soluble or solid-state, that can activate a LiOH-based electrochemistry are compared in detail, with emphasis in providing an updated understanding of the oxygen reduction and evolution reactions in nonaqueous media. We identify the key factors that can switch the cell chemistry between Li 2 O 2 and LiOH and highlight the debate around these routes, as well as rationalize potential causes for these opposing opinions. The identities of the reaction intermediates, activity of redox mediators and additives, location of reaction interfaces, causes of parasitic reactions, as well as the effect of CO 2 on the LiOH electrochemistry, all play a critical role in altering the relative rates of ...

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The kinetics of the oxygen—peroxide couple on carbon

Cited by 85 publications

References 6 publications

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

Electrochemistry at Highly Oriented Pyrolytic Graphite (HOPG): Toward a New Perspective

Recent Progress in Developing a LiOH‐Based Reversible Nonaqueous Lithium–Air Battery

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