Experimental and Theoretical Study of Concentration Distributions in a Model Pore Electrode: II . Mathematical Models and Comparison to Experiment

Weaver, Jeffrey K.; McLarnon, Frank; Cairns, Elton J.

doi:10.1149/1.2086020

Cited by 9 publications

(10 citation statements)

References 12 publications

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“…This electrode is constructed so that a thin film of electrolyte lies on a planar Zn electrode, and a transparent cover glass permits in situ microscopy of the electrode surface as electrodissolution proceeds. This technique was first used by Katan and co-workers to study Type I film formation on Zn (516)(517)(518), and has since been used by others (519)(520)(521). The film precipitation is seen as a "front" that moves from the mouth of the pore to its root as the discharge proceeds.…”

Section: Fundamental Studiesmentioning

confidence: 99%

“…The film precipitation is seen as a "front" that moves from the mouth of the pore to its root as the discharge proceeds. Weaver et al have extended this technique by using probe beam deflection to measure local concentration gradients in the pore (521). Figure 7 shows a schematic diagram of a model pore cell with probe beam deflection.…”

Section: Fundamental Studiesmentioning

confidence: 99%

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The Secondary Alkaline Zinc Electrode

McLarnon

Cairns

1991

J. Electrochem. Soc.

450

328

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Zinc is the most commonly used battery electrode, and zinc primary batteries have found numerous applications. The zinc electrode is electrochemically reversible in alkaline electrolytes, and there is a strong incentive to develop a practical secondary battery based on this metal. However, secondary batteries that use zinc electrodes typically exhibit short lifetimes, because of problems with zinc material redistribution and undesirable zinc morphologies that form during recharge. There has been a worldwide effort to develop a long-lived secondary alkaline zinc electrode, and marked improvements in cell lifetimes have resulted. This article reviews these efforts, paying particular attention to research and development during the period 1975-1990.

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Section: Fundamental Studiesmentioning

confidence: 99%

Section: Fundamental Studiesmentioning

confidence: 99%

The Secondary Alkaline Zinc Electrode

McLarnon

Cairns

1991

J. Electrochem. Soc.

450

328

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“…An electrochemical cell with a horizontal upward-facing Zn anode nearby a plan-parallel Ni(OH) 2 /NiOOH electrode has been used frequently in order to suppress the natural convection induced by buoyancy forces. [22][23][24][25] Eisenberg pointed out the importance of natural convection and diffusion under gravity field effects. 26 We also recognized natural convection was very important, especially considering the use of a secondary battery for large-scale storage in an electrical energy network system.…”

mentioning

confidence: 99%

Coupling Phenomena between Zinc Surface Morphological Variations and Ionic Mass Transfer Rate in Alkaline Solution

Arise

Kawai

Fukunaka

et al. 2012

J. Electrochem. Soc.

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A horizontal upward-facing Zn anode was electrochemically dissolved in aqueous alkaline electrolyte. A plane-parallel upwardfacing Ni(OH) 2 /NiOOH cathode was combined with the Zn anode in a single cell, divided by a polymer separator. This configuration can be regarded as a single pore model inside the porous space of a Zn-NiOOH battery cell. It also insures that the ionic mass transfer rate by diffusion and migration mechanism is dominant over that by natural convection. The morphological variations of the Zn anode surface were examined during the discharge operation of the Zn-NiOOH model cell. Two-dimensional transient concentration profiles of each ion accompanying the electrochemical dissolution of Zn anode in alkaline electrolyte were numerically calculated. The surface morphological variations of the Zn anode were discussed with the aid of numerical simulation. ZnO precipitation on the Zn anode surface was confirmed to be dependent on the horizontal distance from the separator. The present numerical model provides insight to the analysis of observed morphological variations along the Zn anode surface.Rechargeable batteries for electric vehicle (EV) and hybrid electric vehicle (HEV) applications have been a subject of intense focus for the last decade or so. Although Li-based systems have received the most attention, there has been increasing interest in Zn-based systems because of their lower costs, material abundance, and compatibility with nonflammable aqueous electrolytes. When a Zn anode is used in a secondary battery, its morphological variations introduce some serious problems of short life, poor reliability, and safety issues. The coupled phenomena between ionic mass transfer rates and electrode surface morphological variations must be well understood, in order to develop a fully optimized rechargeable Zn battery.The ultimate goal of our studies is to incorporate the fundamental knowledge of Zn electrochemical processes into a numerical model for a hybrid electric vehicle (HEV) battery as well as large-scale battery operation. The model may predict optimal conditions for operations such as high-rate, short-duration, shallow charge/discharge cycles in alkaline solution. In addition, it can provide a new insight to control HEV batteries for the depletion of hydroxide (OH − ) ion at rates greater than 10 mA/cm 2 .Many researchers have studied the surface morphological variations of Zn anodes in alkaline solution over the past few decades. Powers and Breiter first studied the surface morphology of ZnO precipitates by optical microscopy. 1 They classified ZnO into two categories as type I and type II films. Type I films are white, loose, and flocculent, and they appear to homogeneously precipitate in a supersaturated solution layer of zincate (Zn(OH) 4 2− ) ion near the electrode surface in the absence of convection. Type II films are light gray to black, more compact, and appear to form directly on the surface rather than by homogeneous precipitation in the absence of convection.Szpak and Gabriel carri...

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“…Generally, electrochemical intercalation consists of two coupled processes: insertion of an ionic intercalant and a change in the host's electronic structure. The flux of ionic species during intercalation can be monitored using electroanalytical techniques specially designed for this, for example, probe beam deflection (or “mirage”) technique (PBD) − and electrochemical quartz-crystal microbalance (EQCM). − Moreover, application of different techniques, such as in situ resistometry, may result in better characterization of the flux of electronic species. Thus, these two groups of in situ techniques are complementary with regard to their application for studying intercalation mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Dilute Graphite−Sulfates Intercalation Stages Studied by Simultaneous Application of Cyclic Voltammetry, Probe-Beam Deflection, In situ Resistometry, and X-ray Diffraction Techniques

Levi¹,

Levi²,

Gofer³

et al. 1999

J. Phys. Chem. B

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This paper describes the stoichiometry, kinetics, and electronic resistivity of dilute graphite−sulfates intercalation compounds (stages pristine toVIII) obtained during electrochemical oxidation of graphite in 4M H2SO4 solution. The stoichiometry of the reaction was determined by the use of cyclic voltammetry and in situ XRD. Dilute graphite-sulfates phases are formed continuously as solid solution in the graphite matrix. The electronic resistivity of the composite graphite electrode as a function of potential depends largely on parasitic reactions, i.e., partial oxidation of graphite particles. The ionic flux of the HSO4 - species across the electrode−solution interface was traced by deflection of a probe-laser beam (“mirage”, or PBD technique) measured simultaneously with cyclic voltammetry. Convolution of the resulting deflectograms, measured at different distances from the electrode, allowed the calculation of diffusion coefficient of the active species in solution. Basic electroanalytical features of Li-ion intercalation into graphite from Li+-containing aprotic electrolytes are compared with those for HSO4 - in aqueous 4M H2SO4.

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Experimental and Theoretical Study of Concentration Distributions in a Model Pore Electrode: II . Mathematical Models and Comparison to Experiment

Cited by 9 publications

References 12 publications

The Secondary Alkaline Zinc Electrode

The Secondary Alkaline Zinc Electrode

Coupling Phenomena between Zinc Surface Morphological Variations and Ionic Mass Transfer Rate in Alkaline Solution

Dilute Graphite−Sulfates Intercalation Stages Studied by Simultaneous Application of Cyclic Voltammetry, Probe-Beam Deflection, In situ Resistometry, and X-ray Diffraction Techniques

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