An <i>ab initio</i> study for probing iodization reactions on metallic anode surfaces of Li–I<sub>2</sub> batteries

Liu, Zhixiao; Hu, Wangyu; Gao, Fei; Deng, Hui

doi:10.1039/c8ta00356d

Cited by 11 publications

(15 citation statements)

References 51 publications

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“…bond length of the outcast I 2 molecule is 2.86 Å, which is only 0.2 Å longer than that of the free I 2 molecule. 53 Figure 6a shows the net charge variation of I atoms repulsed by the substrate. At 0.15 ps, both of them are charged by −0.5|e| because they are near to the Mg surface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Previous theoretical and experimental studies have demonstrated that LiNO 3 additive can protect the metallic Li anode in Li−S batteries 62−64 and Li−I 2 batteries. 53,65 Inspired by these efforts, the present study also evaluates Mg(NO 3 ) 2 as the electrolyte additive for protecting the Mg(0001) surface. Our AIMD simulation demonstrates that Mg(NO 3 ) 2 can be reduced by the Mg surface and form a thin magnesium oxynitride layer.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Liu¹,

Hu³

et al. 2018

J. Phys. Chem. C

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Metallic anodes in Li/Na–X (X = S, Se, I2) batteries, in which the working mechanism is a conversion reaction, suffer severe corrosion and self-discharge caused by the shuttle effect. Beyond alkali metals, magnesium is also considered as the next-generation metallic anode for secondary batteries. The present study used atomic-scale modeling strategies to reveal the iodization reaction on the anode surface in the Mg–I2 battery. Under the low-coverage condition (Θ = 12.5%), the Mg(0001) surface can provide strong chemical bonding interaction to the I2 molecule, and the dissociation and reduction of I2 to I– anions are thermodynamically and kinetically preferred. Ab initio molecular dynamics simulations demonstrate that a partially iodized layer forms on the anode surface under the high iodine coverage condition (Θ = 100%), and this layer excludes the rest of the I2 molecules after the iodization. The ultrahigh iodine coverage (Θ = 200%) can also generate the partially iodized Mg surface which excludes I2 molecules. However, the ultrahigh coverage also results in great surface reconstruction, which potentially leads to the loss of Mg. According to the present simulation, Mg(NO3)2 is helpful for forming a thin and robust magnesium oxynitride protecting layer on the fresh Mg anode. This protecting layer can block the interaction between the Mg anode and I2 shuttled from the cathode side. The present theoretical study reveals that the Mg anode shows good resistance to iodization-induced corrosion and self-discharge, and the Mg(NO3)2 treatment can further improve the performance of the metallic anode in the Mg–I2 battery.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Liu¹,

Hu³

et al. 2018

J. Phys. Chem. C

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“…Thus, the dissolved iodine species will uncontrollably shuttle to the anode and react with the anode, causing low Coulombic efficiency, severe self‐discharge, and a short cycling life. [ 47,48 ]…”

Section: Operational Mechanisms and Shuttle Effect Of Novel Esssmentioning

confidence: 99%

Boosting Energy Storage via Confining Soluble Redox Species onto Solid–Liquid Interface

Sun

Liu

Zhang

et al. 2021

Advanced Energy Materials

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An upswell in the demand for both high energy density and large power density has triggered extensive research in developing next‐generation energy storage systems (ESSs), including redox‐enhanced electrochemical capacitors, metal–sulfur (LiS and NaS) batteries, and metal–iodine (LiI2, NaI2, etc.) batteries, which involve a liquid reaction pathway that decouples the reaction kinetics from the sluggish ion diffusion in the solid phase. Development is plagued at present by the shuttle effects of soluble redox species (SRSs) resulting in poor cycling stability and rapid self‐discharge. Based on the shuttle mechanisms of SRSs, it is crucial to build an atomic or molecular relationship between the electrode surface and SRSs, that is, solid–liquid interface. Here, a timely review of current advances towards the confinement of SRSs in ESSs through solid–liquid interfacial manipulation at the atomic/molecular level is presented. Particularly, the immobilization mechanisms of SRSs around electrode materials within a series of successful examples are highlighted. The corresponding promising research avenues and challenges via interfacial manipulations are also outlined. With this work as a background, new insights into promising strategies that effectively confine the SRSs around electrodes are discussed, with the aim to facilitate vertical leaps in the performance of next‐generation ESSs.

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“…Lithium metal surface is known to be active and is prone to react with the small gas molecules present in its environment [47,48] . Zavadil and Armstrong have made significant contribution to explore the chemistry of small molecules on lithium surface [49,50] .…”

Section: Introductionmentioning

confidence: 99%

“…[46] Lithium metal surface is known to be active and is prone to react with the small gas molecules present in its environment. [47,48] Zavadil and Armstrong have made significant contribution to explore the chemistry of small molecules on lithium surface. [49,50] The work carried out to determine the rate of passivation of lithium metal with the exposure of environmental gases clearly advocates the high susceptibility of lithium towards these gases.…”

Section: Introductionmentioning

confidence: 99%

Dissociative Adsorption of H₂S on Li(110) Surface Using Density Functional Theory Calculations and Car‐Parrinello Molecular Dynamics Simulations

2021

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The information concerning dissociative adsorption of H2S on Li surface is inadequate and the mechanistic insight for its complete dissociation is yet to be explored. The present investigation aims to scrutinize the dissociative adsorption of H2S on Li(110) surface using density functional theory calculations. The climbing image nudged elastic band calculation was employed to unveil the relative energy profiles for S−H dissociation. To elucidate the components of interaction energy responsible for stabilizing the adsorbed moieties on the surface, periodic energy decomposition analysis was performed. A Car‐Parrinello molecular dynamics (CPMD) simulation was performed to understand the dynamic behaviour of H2S on Li(110). Results vividly demonstrates: (i) partially dissociated product with perpendicular S−H is comparatively stable than the parallel SH, (ii) completely dissociated moieties H/H/S are the most stable among all, (iii) dissociation of first S−H is barrierless and the second S−H dissociation is a low energy barrier reaction, (iv) complete dissociation of H2S occurs in a stepwise manner, (v) orbital and electrostatic contributions of the interaction energy plays a vital role in stabilizing the dissociated moieties, and (vi) stepwise dissociation of H2S was further reinforced by CPMD.

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An ab initio study for probing iodization reactions on metallic anode surfaces of Li–I₂ batteries

Abstract: A Li oxynitride protecting layer produced by the LiNO3 additive can prohibit surface iodization and LiI exfoliation.

Cited by 11 publications

References 51 publications

Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Boosting Energy Storage via Confining Soluble Redox Species onto Solid–Liquid Interface

Dissociative Adsorption of H₂S on Li(110) Surface Using Density Functional Theory Calculations and Car‐Parrinello Molecular Dynamics Simulations

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An ab initio study for probing iodization reactions on metallic anode surfaces of Li–I2 batteries

Abstract: A Li oxynitride protecting layer produced by the LiNO3 additive can prohibit surface iodization and LiI exfoliation.

Cited by 11 publications

References 51 publications

Does the Mg–I2 Battery Suffer Severe Shuttle Effect?

Does the Mg–I2 Battery Suffer Severe Shuttle Effect?

Boosting Energy Storage via Confining Soluble Redox Species onto Solid–Liquid Interface

Dissociative Adsorption of H2S on Li(110) Surface Using Density Functional Theory Calculations and Car‐Parrinello Molecular Dynamics Simulations

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An ab initio study for probing iodization reactions on metallic anode surfaces of Li–I₂ batteries

Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Does the Mg–I₂ Battery Suffer Severe Shuttle Effect?

Dissociative Adsorption of H₂S on Li(110) Surface Using Density Functional Theory Calculations and Car‐Parrinello Molecular Dynamics Simulations