Can a Transport Model Predict Inverse Signatures in Lithium Metal Batteries Without Modifying Kinetics?

Uppaluri, Maitri; Subramaniam, Akshay; Mishra, Lubhani; Viswanathan, Vilayanur V.; Subramanian, Venkat R.

doi:10.1149/1945-7111/abd2ae

Cited by 8 publications

(11 citation statements)

References 28 publications

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“…In general, two classes of Li plating mechanisms have been discussed. , The first uses classical models describing dendritic deposition of nonreactive metals. − This class attributes large gradients of Li + concentration in the electrolyte during fast charging as the main cause of dendritic growth. ,− Ramified growth of Li at Sand’s time (when Li + surface concentration reaches 0) has partially validated this idea, but requisite current densities ( J ) generally exceed typical battery operations. Furthermore, the reactivity of Li and the solid electrolyte interphase (SEI)a nanometers-thick and ionically conductive passivation filmare neglected.…”

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confidence: 99%

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes

Boyle

Pei

et al. 2022

Nano Lett.

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Poor fast-charge capabilities limit the usage of rechargeable Li metal anodes. Understanding the connection between charging rate, electroplating mechanism, and Li morphology could enable fast-charging solutions. Here, we develop a combined electroanalytical and nanoscale characterization approach to resolve the current-dependent regimes of Li plating mechanisms and morphology. Measurement of Li+ transport through the solid electrolyte interphase (SEI) shows that low currents induce plating at buried Li||SEI interfaces, but high currents initiate SEI-breakdown and plating at fresh Li||electrolyte interfaces. The latter pathway can induce uniform growth of {110}-faceted Li at extremely high currents, suggesting ion-transport limitations alone are insufficient to predict Li morphology. At battery relevant fast-charging rates, SEI-breakdown above a critical current density produces detrimental morphology and poor cyclability. Thus, prevention of both SEI-breakdown and slow ion-transport in the electrolyte is essential. This mechanistic insight can inform further electrolyte engineering and customization of fast-charging protocols for Li metal batteries.

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confidence: 99%

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes

Boyle

Pei

et al. 2022

Nano Lett.

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“…To characterize the time evolution of electrolyte thickness, Eq. [24] can be used as 𝐿(𝑡) 𝐿(0) = 𝜌 𝑐(𝑥, 0) 1 𝐿(𝑡) ∫ 𝜌 ( ) d𝑥 = 𝜌 𝑐(𝑥, 0) 𝜌 , [27] where the salt concentration is to compute the density profile at every time instance.…”

Section: Discussionmentioning

confidence: 99%

“…We, therefore, neglect the relative motion of the plating electrode. This is an important assumption since it avoids coordinate transformation associated with moving boundary problems [23][24][25] . Thus, the plating boundary conditions simplify to…”

Section: Boundary Conditionsmentioning

confidence: 99%

Effect of Solvent Motion on Ion Transport in Electrolytes

Mistry

Grundy

Halat

et al. 2022

J. Electrochem. Soc.

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We use concentrated solution theory to derive an equation governing solvent velocity in a binary electrolyte when a current passes through it. This equation in combination with the material balance equation enables the prediction of electrolyte concentration profiles and ion velocities as a function of space and time. This framework is used to predict ion velocities in Li-Li symmetric cells containing a mixture of lithium bis(trifluoromethanesulfonyl)imide and poly(ethylene oxide) (LiTFSI/PEO), for which the cation transference number relative to the solvent velocity, t_+^0, can be either positive or negative in LiTFSI/PEO mixtures, depending on salt concentration. Accounting for the solvent motion is increasingly important at higher concentrations. Especially for negative t_+^0, if solvent velocity is set to zero, the cation velocity, based on the electrode-electrolyte interface reference frame, is pointed opposite to the current flow. However, when solvent motion is taken into account, the cation velocity, based on the same reference frame, is in the same direction as the current. This analysis demonstrates the importance of accounting for solvent velocity rigorously in seemingly simple systems such as symmetric cells.

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“…Similar variations in the cell potential upon the change in Li electrode morphology are widely reported in the literature. [27][28][29] Unlike others, Uppaluri et al 30 have explained the decay in cell potential without modifying the reaction kinetics in a Li-Li symmetric cell operating near the limiting current density. The inverse signatures intensified with higher resistance to the diffusion of Li + ions.…”

Section: Variable Equation Boundary Conditionsmentioning

confidence: 99%

“…28 Subramaniam et al 29 observed a similar voltage response during plating with the fitted exchange current density marking the shift in reaction kinetics. 29 Later, Uppaluri et al 30 used the moving boundary condition to predict the inverse voltage signatures due to the mass-transfer limitations.…”

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confidence: 99%

Insights into the Morphological Evolution of Mossy Dendrites in Lithium Metal Symmetric and Full Cell: A Modelling Study

Verma

Puravankara²,

Nandanwar³

et al. 2023

J. Electrochem. Soc.

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Mossy-dendrite growth is a common phenomenon observed in many lithium metal batteries. A lattice model is presented in this work to understand the morphological changes in mossy dendrites during the plating and stripping of Li metal. The model mimics the mossy growth by incorporating nucleation and growth of spherical particles at lattice points. The model can predict the transition between root and tip growth by merely changing the Damköhler number. The mass transfer limitations created by the initiation of the mossy phase are identified as the dominant cause of the decay in cell potential. We also investigate the effect of morphology on the formation of dead lithium during electrodissolution. This is the first attempt to combine pseudo-2D and lattice models to simulate full-cell cycles toward mossy growth.

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Can a Transport Model Predict Inverse Signatures in Lithium Metal Batteries Without Modifying Kinetics?

Cited by 8 publications

References 28 publications

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes

Effect of Solvent Motion on Ion Transport in Electrolytes

Insights into the Morphological Evolution of Mossy Dendrites in Lithium Metal Symmetric and Full Cell: A Modelling Study

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