Lithium dendrite growth mechanisms in liquid electrolytes

Jana, Aniruddha; Garcı́a, R. Edwin

doi:10.1016/j.nanoen.2017.08.056

Cited by 165 publications

(106 citation statements)

References 55 publications

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“…Holes can be seen on the fluorine caps as predicted by the isodensity surface We can infer, at least in part, the existence of σ-holes in these molecules, even if only exhibited over a small range. For neutral PF 6 , moving over a short range from ±0.30 to ±0.35 V gives us a fleeting instance of a σ-hole, which disappears quickly as we reach nuclear domain potentials close to the atoms ( Figure 5). We can infer, at least in part, the existence of σ-holes in these molecules, even if only exhibited over a small range.…”

Section: Resultsmentioning

confidence: 99%

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Sigma-Holes in Battery Materials Using Iso-Electrostatic Potential Surfaces

et al. 2018

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Abstract:The presence of highly electronegative atoms in Li-ion batteries anticipates the formation of σ-hole regions that may strongly affect the ionic conductivity. The σ-hole consists of a region of positive electrostatic potential extending in the direction of the covalent bond between atoms of groups IV-VII due to anisotropic charge distribution. Graphite electrodes in Li-ion batteries that become halogenated due to the electrolyte, as well as some solid electrolyte materials, can exhibit these σ-holes. Since Li-ions should be able to drift in any part of the battery, the fact that they can be attracted and eventually absorbed by regions of strong negative potentials produced by high-electronegativity counterions becomes detrimental to ionic conductivity. Therefore, the presence of positive well-defined regions, repulsive to the Li-ions, might act as lubricant for Li-ions drifting through electrolytes, thus improving the Li-ion conductivity. In addition, the σ-holes might also have a strong effect on the formation of the passivating layer, known as the solid electrolyte interphase (SEI) at electrode surfaces, which is of paramount importance for the performance of rechargeable batteries. Here we investigate the existence of σ-holes on surfaces of graphite anodes and of a few solid electrolytes by examining the electrostatic potentials calculated using density functional theory.

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Section: Resultsmentioning

confidence: 99%

“…To some extent, the σ-hole was observed when fluorine was tested (Figure 7). Fluorine comes directly from the decomposition of PF 6 − on the surface or about the electrode, producing a σ-hole from −2.80 to −2.75 V; for other potentials there is no sigma-hole formation.…”

Section: Resultsmentioning

confidence: 99%

Sigma-Holes in Battery Materials Using Iso-Electrostatic Potential Surfaces

et al. 2018

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“…[3,[13][14][15][16] These routes for suppressing "dendrites" or mossy lithium formation typically rely on the theoretical considerations, which were suggested decades ago, but are still in focus in current reviews. [14][15][16] At the same time recent observations of competing tip and root growth of lithium needles [17][18][19][20][21] and its microstructure revealed by cryo-TEM [22] contradict with many of suggested theoretical models.…”

Section: Electromigration In Lithium Whisker Formation Plays Insignifmentioning

confidence: 96%

“…In contrast to graphite, which has nearly constant surface area stabilized by a solid-electrolyte interphase (SEI) upon the first few lithiation cycles, "dendrites" create new surface in each cycle, thus the electrolyte is being continuously consumed for SEI formation on each battery charge. [14][15][16] At the same time recent observations of competing tip and root growth of lithium needles [17][18][19][20][21] and its microstructure revealed by cryo-TEM [22] contradict with many of suggested theoretical models. [3] In addition, non-uniform metal deposition leads to capacity loss due to so-called "dead lithium", which forms when such needle-or bush-like structures dissolve at the base during discharge and loose electrical contact with the electrode.…”

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Electromigration in Lithium Whisker Formation Plays Insignificant Role during Electroplating

et al. 2019

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Alexey A. Rulev, [a, b] Artem V. Sergeev, [a, c] Lada V. Yashina, [a] Timo Jacob, [d, e, f] and Daniil M. Itkis* [a] Plating of metallic Li results in deposition of needle-like structures, whose prevention is a fundamental challenge that currently restricts the development and application of high energy Li-metal rechargeable batteries. Over the last decades, a number of mechanisms were proposed to explain morphological instabilities of planar crystallization fronts. The suggested reasons for non-uniform deposition include Li + concentration gradients in the nutrient phase, accelerated electromigration to the tip of the growing needle, specific nucleation behavior, mechanical properties of the solid-electrolyte interphase, and many more. Here, we unravel the role of electromigration currents by adding indifferent cations (TBA + , TEA + ) to screen for non-uniform electric fields, thus, suppressing migrationdriven mass-transfer. Nearly full exclusion of electromigration currents showed no impact on the morphology of electrodeposited lithium. Therefore, the role of electromigration seems negligible, and electric field edge effects are undoubtedly not the main driving force for filament growth during Li plating.Today, lithium-ion batteries are the most wide-spread portable electrochemical energy storage devices. Often referred to as "rocking chair" battery, typical lithium-ion cell operation is enabled by movement of lithium ions from the negative (anode) to the positive electrode (cathode), while the reverse process occurs during charging. [1] [a] A. A. Rulev, Dr. A. V. Sergeev, Dr. glovebox with less than 0.1 ppm H 2 O and O 2 concentrations. The electrochemical measurements were performed with a BioLogic SAS SP-300 potentiostat/galvanostat.

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Enabling Stable Lithium Metal Anode through Electrochemical Kinetics Manipulation

Han

Jie

Huang

et al. 2019

Adv Funct Materials

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The surface morphology of Li metal anode significantly dictates the stability and safety of Li metal batteries. The key parameters for morphological control and causes for dendritic growth of Li anode are still not clear. Although the plating kinetics is generally believed to be associated with Li growth habits, the detailed models are still not well defined. In this work, the temperature effect on the stability and efficiency of Li anode is systematically investigated in a variety of electrolyte composition for Li metal batteries. A dendrite‐free growth mechanism is observed, and a high Coulombic efficiency up to ≈99.4% in Li||Cu cells is achieved by tuning the deposition behaviors at elevated temperatures. The results provide insights into the Li dendrite growth mechanism and general principle for developing stable Li anode.

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Lithium dendrite growth mechanisms in liquid electrolytes

Cited by 165 publications

References 55 publications

Sigma-Holes in Battery Materials Using Iso-Electrostatic Potential Surfaces

Sigma-Holes in Battery Materials Using Iso-Electrostatic Potential Surfaces

Electromigration in Lithium Whisker Formation Plays Insignificant Role during Electroplating

Enabling Stable Lithium Metal Anode through Electrochemical Kinetics Manipulation

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