Electrochemistry of Intercalation Materials Charge‐Transfer Reaction and Intercalate Diffusion in Porous Electrodes

Verbrugge, Mark W.; Koch, Brian J.

doi:10.1149/1.1391689

Cited by 57 publications

(55 citation statements)

References 26 publications

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“…3a represents the cell current (i) plotted against the applied cell voltage (E) and normalized with respect to the cathode's active material mass. The intercalation/de-intercalation reactions that lead to this current have the following general form [18].…”

Section: Cyclic Voltammetry and Faradaic Reactions Of Surface Filmsmentioning

confidence: 99%

Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries

Crain

Zheng

Sulyma

et al. 2012

J Solid State Electrochem

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Lithium manganese oxide (LMO), mechanochemically modified by ball-milling, is a potentially useful active material for high-power-density cathodes of lithium ion batteries. The present work investigates the electrochemical characteristic of a cathode prepared from a controlled mixture of nano-and micrometric LMO particles processed in this approach. The nanoparticles in the mixture support surface-localized insertion/extraction of Li and thus increase the cathode charge/discharge rates. The LMO microparticles promote cathode cyclability by stabilizing the coexisting nanoparticles against segregation and strong electrolyte reactions. The underlying mechanisms of these effects are studied here using voltammetry, galvanostatic cycling, Ragone plot construction, and electrochemical impedance spectroscopy. The relative timescales of charge transfer and diffusion of Li + within the LMO lattice are determined, and the criteria for material utilization during rapid charge-discharge are examined.

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Section: Cyclic Voltammetry and Faradaic Reactions Of Surface Filmsmentioning

confidence: 99%

Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries

Crain

Zheng

Sulyma

et al. 2012

J Solid State Electrochem

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“…Construction of pulse polarization curves from pulse discharge simulations.-Utilizing Newman's model in Comsol Multiphysics 3.5a [2][3][4][5][11][12][13][14][15][16][17][18][19][20] and fitting it to the experimental data 1,26 based on the four previously described factors (diffusivity 17 and kinetic rate constant [13][14][15][16]21 for each electrode), we constructed PPCs. We also created PPCs that were predicted by the model but were not experimentally validated.…”

Section: Resultsmentioning

confidence: 99%

Pulse Polarization for Li-Ion Battery under Constant State-of-Charge: Part II. Modeling of Individual Voltage Losses and SOC Prediction

DuBeshter¹,

Jorné²

2017

J. Electrochem. Soc.

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A Li-Ion battery, as most batteries, is an unsteady state system. In order to generate polarization curves under constant state of charge (SOC), an experimentally tedious task, we used a pulse discharge method where the initial SOC was adjusted such that at the end of the pulse and during the relaxation the SOC is pre-determined and constant. In this paper the pulse discharge data were simulated using Newman's model, allowing the identification of individual overpotentials under various discharge times, C-rates, and SOC. The agreement between the model and experimental results allowed the construction of pulse polarization curves (PPC) and the identification of individual overvoltages: charge transfer kinetics, ionic mass transport, and solid-state diffusion. The pulse polarization curves converged by the 240 seconds pulse discharge, forming a quasi steady-state polarization curve for the battery, which can be used to determine the SOC of a battery by measuring its steady voltage and current density. In electric cars this method can resolve the driver's range anxiety associated in accurately determining the SOC, especially at low SOC. In a previous paper, 1 we experimentally explored the pulse discharge method in Lithium Ion Battery (LIB) and the ability to generate pulse polarization curves (PPC) from that data at discrete states of charge (SOC) and various pulse durations. As mentioned 1 studying battery voltage vs current density 1-6 remains difficult, in part since the SOC changes as the battery is used. Previous work experimentally evaluates a voltage vs current density relationship at a constant SOC.1 In this paper, we use the Newman model 2,3 and COMSOL Multiphysics 4,5 to expand predictions about PPC behavior as pulse times increase reaching pseudo steady state polarization. Bernardi and Go 6 also utilized a pulse discharge method to gather data and a similar model to analyze the performance and voltage evolution, and the modeled results matched very well with their experimental data.In contrast, this work compared the voltages at the end of the pulse discharge and after the battery had returned to an equilibrium at rest state. This allowed us to expand the SOC testing to 10%, 40%, and 70%, from previously reported 6 range of 35% and 65%. Additionally, this model relied on fewer calculated parameters, and could only fit the kinetic rate constant and diffusion in the active particles of the electrode materials. While this involved more experimental results for a battery archetype, the resulting model was usable over a wider range of SOC and performance scenarios than previously demonstrated. This allowed the study of what conditions would allow a battery to achieve a quasi steady state, which is useful for performance analysis and SOC prediction.From a conceptual point of view, a short pulse discharge exhibits voltage losses most attributed to charge transfer kinetic and ohmic losses. As the pulse discharge times increase, the voltage losses increasingly depend on the Li + concentration gradient forming f...

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“…(28), the coefficient in parentheses in Eq. (38) has the units of mobility, but it can also be expressed using an equivalent diffusion coefficient.…”

Section: Immobile Hostmentioning

confidence: 99%

“…For lithiated electrode materials, the insertion of a lithium-ion from an electrolytic solution into the particle as a neutral molecule of species 1 is described by Eq. (33) where i=1 [31,[35][36][37][38][39]. The chemical potential of the lithium reference electrode is a constant and serves as a reference value that enables the determination of μ 1 −μ 3 .…”

mentioning

confidence: 99%

Thermodynamics, stress, and Stefan-Maxwell diffusion in solids: application to small-strain materials used in commercial lithium-ion batteries

Baker

Bower

2015

J Solid State Electrochem

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The life and performance of lithium-ion batteries are related to the mechanical expansion and contraction of the active materials. We develop a theory and commensurate equations to describe how lithium diffuses within host materials; our focus is clarifying the influence of stress on solidstate diffusion processes. Small-strain mechanics are combined with diffusion processes described by the StefanMaxwell equations. For the first time, to our knowledge, we compare host materials in which (a) both the host and lithium guest species diffuse with (b) the conventional approach based on guest (lithium) diffusion only. We describe the merits and weaknesses of our treatment with those that exist today, and we outline improvements to be addressed in subsequent work.

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Electrochemistry of Intercalation Materials Charge‐Transfer Reaction and Intercalate Diffusion in Porous Electrodes

Cited by 57 publications

References 26 publications

Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries

Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries

Pulse Polarization for Li-Ion Battery under Constant State-of-Charge: Part II. Modeling of Individual Voltage Losses and SOC Prediction

Thermodynamics, stress, and Stefan-Maxwell diffusion in solids: application to small-strain materials used in commercial lithium-ion batteries

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