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JournalISSN: 0013-4651

Journal of The Electrochemical Society 

About: Journal of The Electrochemical Society is an academic journal. The journal publishes majorly in the area(s): Electrolyte & Oxide. It has an ISSN identifier of 0013-4651. Over the lifetime, 47082 publication(s) have been published receiving 1560790 citation(s).
Topics: Electrolyte, Oxide, Silicon, Lithium, Thin film
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Journal ArticleDOI
Abstract: Reversible extraction of lithium from LiFePO 4 (triphylite) and insertion of lithium into FePO 4 at 3.5 V vs. lithium at 0.05 mA/cm 2 shows this material to be an excellent candidate for the cathode of a low-power, rechargeable lithium battery that is inexpensive, nontoxic, and environmentally benign. Electrochemical extraction was limited to ∼0.6 Li/formula unit; but even with this restriction the specific capacity is 100 to 110 mAh/g. Complete extraction of lithium was performed chemically; it gave a new phase, FePO 4 , isostructural with heterosite, Fe 0.65 Mn 0.35 PO 4 . The FePO 4 framework of the ordered olivine LiFePO 4 is retained with minor displacive adjustments. Nevertheless the insertion/extraction reaction proceeds via a two-phase process, and a reversible loss in capacity with increasing current density appears to be associated with a diffusion-limited transfer of lithium across the two-phase interface. Electrochemical extraction of lithium from isostructural LiMPO 4 (M = Mn, Co, or Ni) with an LiClO 4 electrolyte was not possible; but successful extraction of lithium from LiFe 1-x Mn x PO 4 was accomplished with maximum oxidation of the Mn 3+ /Mn 2+ occurring at x = 0.5. The Fe 3+ /Fe 2+ couple was oxidized first at 3.5 V followed by oxidation of the Mn 3+ /Mn 2+ couple at 4.1 V vs. lithium. The Fe 3+ -O-Mn 2+ interactions appear to destabilize the Mn 2+ level and stabilize the Fe 2+ level so as to make the Mn 3+ /Mn 2+ energy accessible.

6,469 citations

Journal ArticleDOI

2,893 citations

Journal ArticleDOI
Abstract: We present here an isothermal, one-dimensional, steady-state model for a complete polymer electrolyte fuel cell (PEFC) with a 117 Nation | membrane. In this model we employ water diffusion coefficients electro-osmotic drag coefficients, water sorption isotherms, and membrane conductivities, all measured in our laboratory as functions of membrane water content. The model pre.dicts a net-water-per-proton flux ratio of 0.2 H20/H § under typical operating conditions, which is much less than the measured electro-osmotic drag coefficient for a fully hydrated membrane. It also predicts an increase in membrane resistance with increased current density and demonstrates the great advantage of a thinner membrane in alleviating this resistance problem. Both of these predictions were verified experimentally under certain conditions.

2,765 citations

Journal ArticleDOI
Milton Stern1, A. L. Geary1
Abstract: At low overvoltage values, deviations from Tafel behavior for a noncorroding electrode are due primarily to the reverse reaction of the oxidation‐reduction system, and at high overvoltages to concentration and/or resistance polarization. It is shown further that the practice of placing straight lines through a few experimental points is extremely hazardous, while the indiscriminate introduction of "breaks" is contrary to the electrode kinetics described.Further complexities arising from a corroding electrode are described. In this instance, the forward and reverse reactions of both of the oxidation‐reduction systems forming the corrosion couple must be considered. This representation of the local polarization diagram of a corroding metal is more fundamental than that used previously in the literature, and thus provides a clearer picture of the various factors which affect the corrosion rate and the shape of polarization curves.A region of linear dependence of potential on applied current is described for a corroding electrode by treating it in a manner analogous to that for a noncorroding electrode. An equation is derived relating the slope of this linear region to the corrosion rate and Tafel slopes. This relation provides an important new experimental approach to the study of the electrochemistry of corroding metals since, in some instances, interfering reactions prevent determination of Tafel slopes at higher current densities.

2,675 citations

Journal ArticleDOI
Abstract: Department of Physics, Technical University Munich, D-85748 Garching, GermanyA density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition andnoble metals is presented. The bond energies are used to understand the trends in the exchange current for hydrogen evolution. Avolcano curve is obtained when measured exchange currents are plotted as a function of the calculated hydrogen adsorptionenergies and a simple kinetic model is developed to understand the origin of the volcano. The volcano curve is also consistent withPt being the most efficient electrocatalyst for hydrogen evolution.© 2005 The Electrochemical Society. @DOI: 10.1149/1.1856988# All rights reserved.Manuscript submitted May 10, 2004; revised manuscript received August 12, 2004. Available electronically January 24, 2005.

2,623 citations

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Journal's top 5 most impactful authors

J. R. Dahn

399 papers, 36.7K citations

John Newman

205 papers, 22.2K citations

Ralph E. White

191 papers, 11.7K citations

Doron Aurbach

130 papers, 11.8K citations

Hubert A. Gasteiger

129 papers, 12.4K citations