Knowledge on the mechanisms of oxygen reduction reaction (ORR) and descriptors linking the catalytic activity to the structural and electronic properties of transition metal oxides enable rational ...design of more efficient catalysts. In this work ORR electrocatalysis was studied on a set of single and complex Mn(III) oxides with a rotating disc electrode method and cyclic voltammetry. We discovered an exponential increase of the specific electrocatalytic activity with the potential of the surface Mn(IV)/Mn(III) red-ox couple, suggesting the latter as a new descriptor for the ORR electrocatalysis. The observed dependence is rationalized using a simple mean-field kinetic model considering availability of the Mn(III) centers and adsorbate-adsorbate interactions. We demonstrate an unprecedented activity of Mn2O3, ca. 40 times exceeding that of MnOOH and correlate the catalytic activity of Mn oxides to their crystal structure.
Pitfalls in Li-S Rate-Capability Evaluation Poux, Tiphaine; Novák, Petr; Trabesinger, Sigita
Journal of the Electrochemical Society,
01/2016, Letnik:
163, Številka:
7
Journal Article
Recenzirano
Odprti dostop
Rate-capability tests are widely used to highlight advances in Li-S-system development. Here we show, by studying the individual effects of a number of cycling- and electrolyte-related parameters on ...a simple Li-S cell, that the rate-capability results are sensitive not only to the applied current but also to the cycling prehistory of the cell. On the one hand, the performance is affected by the order in which cycling rate is changed. Slow initial rates aggravate material loss and reduce the achievable capacity. On the other hand, the results of rate-capability tests are significantly different when the rates are varied only on the charge or only on the discharge. The charge rate does not directly affect the measured capacity, whereas the discharge rate does, especially when discharge cutoff voltages are high, due to slow discharge reactions. High charge rates, however, do affect the long-term stability, which is difficult to predict from usual rate-capability tests. Our findings also provide insights into the relative reaction rates and the influence of the general cycling procedures, underlining the importance of understanding the kinetics of Li-S systems, while designing them for high performance batteries.
A comparative study of the expansion/shrinking properties of graphite/Si electrodes with different formulations is carried out by means of electrochemical in situ dilatometry. The dilatometry reveals ...the impact of graphite particle size and aspect ratio as well as the binder type on the cycle life of the studied electrode formulations. Two binders, polyvinylidene fluoride (PDVF) and crosslinked carboxymethyl cellulose – polyacrylic acid (CMC/PAA) and two graphites of different particle size and aspect ratios, TIMREX® KS6 and SLP30, are used in composite electrodes and are tested in lithium half cells. The specific charge of electrodes containing Si nanoparticles and PVDF binder declines rapidly in the first cycles. The CMC/PAA based electrodes containing Si exhibit improved cycling stability and better management of dimensional changes occurring during graphite and Si (de)lithiation.
La cinétique lente de la réduction de l’oxygène (ORR) est en grande partie responsable de la perte d’énergie de nombreux systèmes de conversion tels que les piles à combustible. Parmi les possibles ...catalyseurs de l’ORR, les oxydes de type pérovskite sont des candidats prometteurs en milieu alcalin. La présente thèse est consacrée à l’étude de l’activité, du mécanisme et de la stabilité de pérovskites à base de Co et Mn pour l’ORR. Grâce aux techniques d’électrode tournante à disque et disque-anneau (R(R)DE), les études de l’ORR et des transformations d’HO2- sur les couches minces de pérovskite/carbone dans une solution de NaOH ont montré qu’O2 est réduit en OH- via un mécanisme « en série » avec formation d’HO2- intermédiaire. Pour des quantités d’oxyde suffisantes, HO2- est ensuite réduit, ce qui résulte en un mécanisme apparent de 4 électrons. Dans ces électrodes, le carbone joue un double rôle. Il augmente l’activité électrocatalytique en améliorant le contact électrique et il est impliqué dans le mécanisme de l’ORR en catalysant la réduction d’O2 en HO2-, surtout pour les pérovskites à base de cobalt qui sont considérablement moins actives que celles à base de Mn. Néanmoins, l’électrocatalyse de l’ORR semble dégrader les sites actifs des pérovskites.
The sluggish kinetics of the oxygen reduction reaction (ORR) is largely responsible for the energy losses in energy conversion systems such as fuel cells. Among possible inexpensive catalysts for the ORR, perovskite oxides are promising electrocatalysts in alkaline media. The present thesis is devoted to the investigation of the ORR activity, mechanism and stability of some Co and Mn-based perovskites. The rotating (ring) disk electrode (R(R)DE) studies of the ORR and the HO2- transformations on perovskite/carbon thin layers in NaOH electrolyte prove that O2 is reduced to OH- via a “series” pathway with the HO2- intermediate. For high oxide loadings, the formed HO2- species are further reduced to give a global 4 electron pathway. In these electrodes, carbon plays a dual role. It increases the electrocatalytic activity by improving the electrical contact and it is involved in the ORR mechanism by catalyzing the reduction of O2 into HO2-, especially for Co-based perovskites which display lower reaction rates than Mn-based perovskites.
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