Mapping mechanisms and growth regimes of magnesium electrodeposition at high current densities

Davidson, Rachel D.; Verma, Ankit; Santos, David A.; Feng, Hao; Fincher, Cole D.; Zhao, Dexin; Attari, Vahid; Schofield, Parker; Buskirk, Jonathan S. Van; Fraticelli-Cartagena, Antonio; Alivio, Theodore E. G.; Arróyave, Raymundo; Xie, Kelvin Y.; Pharr, Matt; Mukherjee, Partha P.; Banerjee, Sarbajit

doi:10.1039/c9mh01367a

Cited by 90 publications

(63 citation statements)

References 86 publications

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“…In contrast, the five other metals in the lower part of the table have a deposition potential below their pzc, and in the case of Li by more than 1 V. All these metals are prone to dendrite formation—in some solutions this may be obscured by the formation of an insulating passive film. The case of magnesium is controversial, but a very recent study [8] shows that there is always a rough, unwanted surface structure that forms during deposition, which at high current densities takes the shape of dendrites. We shall argue below that the relation between the pzc and the deposition potential is a crucial factor for dendritic growth.…”

Section: Effects Of An Excess Charge Density On the Properties Of An mentioning

confidence: 99%

The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes

Santos

Schmickler

2021

Angew Chem Int Ed

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Much theoretical effort has been spent on the causes of dendrite formation in lithium metal batteries, but a decisive factor has been overlooked: Lithium is deposited on an electrode which carries a sizable negative charge, and this charge is not distributed homogeneously on the surface. We show by explicit model calculations that the excess charge accumulates on small protrusions and creates a strong electric field, which attracts the Li+ ions and induces further growth on the tip and finally the formation of dendrites. Even a small tip consisting of a few atoms will carry an excess charge of a tenth of a unit charge or more. In addition, the negative charge on the tips locally reduces the surface tension, which further fosters dendrite growth. The same principles can also explain dendrite formation on other metals with deposition potentials below the potential of zero charge.

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Section: Effects Of An Excess Charge Density On the Properties Of An mentioning

confidence: 99%

The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes

Santos

Schmickler

2021

Angew Chem Int Ed

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“…However, Al‐ion batteries suffer from several major issues such as dendrite formation, lack of corresponding cathodes, and being nonrechargeable. [ 11–14 ] Apart from dendritic issue, high charge density of Mg, formation of a passivating interfacial layer, and limitation in the choice of cathode and electrolyte have limited application of Mg. [ 15–18 ] Zinc‐metal batteries (ZMBs) are another potential alternative to Li batteries due to numerous benefits such as high energy density (820 mAh g −1 ), less reactivity, multielectron redox capacity allowing for compatibility with aqueous electrolytes, environmental benignity, stability, low equilibrium potential (−0.76 V vs SHE), safety, high abundance, and low cost. [ 19–25 ] As such, ZMBs are considered as a promising candidate for high capacity systems such as grid storage, where aqueous electrolyte‐based systems are widely used.…”

Section: Introductionmentioning

confidence: 99%

Dendritic Zn Deposition in Zinc‐Metal Batteries and Mitigation Strategies

Jabbari

Foroozan

Shahbazian‐Yassar

2021

Adv Energy and Sustain Res

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As one of the most promising energy storage technologies, zinc (Zn)‐metal batteries (ZMBs) have attracted significant attention due to outstanding properties of Zn, including high energy density (820 mAh g−1/5855 mAh cm−3), abundance, low cost, low reactivity, multielectron redox capacity, compatibility with aqueous electrolytes, low equilibrium potential (−0.76 V vs SHE), stability, safety, and environmental benignity. Yet, the existence of some major issues such as surface‐originated parasitic reactions (e.g., corrosion and H2 evolution), formation of dead Zn, and oxide passivation leading to capacity loss in ZMBs are hindering their full potential applications. Addressing these challenges requires profound understanding of mechanism of Zn dendrites formation. Therefore, the aim of the current study is to assess some of the latest challenges and advancements concerning ZMBs, with an emphasis on origin and growth mechanism of Zn dendrites. Herein, it is demonstrated that the Zn electrodeposition does not follow a simple reaction/diffusion limited behavior, and other parameters such as surface energy and surface diffusion barrier play great roles on the morphology and microstructure of the deposited Zn. In addition, recent advances to mitigate Zn dendrite issues by applying modifications on the design of electrode, electrolyte, separator and interface are discussed.

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“…Dagegen liegt bei den fünf Metallen im unteren Teil der Tabelle das Abscheidungspotential unterhalb des Ladungsnullpunkts, im Falle von Lithium um mehr als 1 V. Alle diese Metalle neigen zur Dendritenbildung – in einigen Lösungen mag dies durch die Bildung eines passiven Films verdeckt werden. Der Fall von Magnesium wird zur Zeit kontrovers diskutiert, doch zeigt eine neuere Studie [8] dass sich bei der Abscheidung stets eine raue, unerwünschte Oberflächenstruktur bildet, welche bei höheren Überspannungen die Form von Dendriten annimmt. Wie wir später ausführen werden, ist die Beziehung zwischen pzc und Abscheidungspotential ein entscheidender Faktor bei der Dendritenbildung.…”

Section: Effekte Einer üBerschussladung Auf Die Eigenschaften Einer Eunclassified

Die entscheidende Rolle von lokalen Ladungsfluktuationen beim Wachstum von Dendriten auf Lithium‐Elektroden

Santos

Schmickler

2021

Angewandte Chemie

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Obwohl sich sehr viele theoretische Arbeiten mit der Ursache der Dendritenbildung an reinen Lithium‐Elektroden befasst haben, wurde bisher ein entscheidender Faktor übersehen: Bei der Abscheidung von Lithium ist die Elektrode stark negativ geladen, und diese Ladung ist nicht gleichmäßig über die Oberfläche verteilt. Explizite Modellrechnungen zeigen, dass sich die Überschussladung auf der Spitze kleiner Unebenheiten, die durch Fluktuationen entstehen, konzentriert. Sie erzeugt dort ein starkes elektrisches Feld, welches Lithium‐Ionen anzieht, die Spitze weiter wachsen lässt und schließlich zur Bildung von Dendriten führt. Selbst eine kleine Spitze, die nur aus wenigen Atomen besteht, trägt eine Überschussladung von der Größenordnung eines Zehntels der Elektronenladung oder mehr. Zudem erniedrigt eine negative Ladung lokal die Oberflächenspannung, was die Dendritenbildung zusätzlich begünstigt. Derselbe Mechanismus kann auch die Dendritenbildung an anderen Metallen erklären, deren Abscheidungspotential tiefer liegt als der Ladungsnullpunkt.

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Mapping mechanisms and growth regimes of magnesium electrodeposition at high current densities

Abstract: Galvanostatic electrodeposition from Grignard reagents in symmetric Mg–Mg cells is used to map Mg morphologies from fractal aggregates of 2D nanoplatelets to highly anisotropic dendrites with singular growth fronts and entangled nanowire mats.

Cited by 90 publications

References 86 publications

The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes

The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes

Dendritic Zn Deposition in Zinc‐Metal Batteries and Mitigation Strategies

Die entscheidende Rolle von lokalen Ladungsfluktuationen beim Wachstum von Dendriten auf Lithium‐Elektroden

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