Electrolyte Additive Enabling Conditioning-Free Electrolytes for Magnesium Batteries

Kang, Sanggil; Kim, Hyeonji; Hwang, Sunwook; Jo, Minsang; Jang, Moongyu; Park, Changhun; Hong, Seung‐Tae; Lee, Hochun

doi:10.1021/acsami.8b13588

Cited by 45 publications

(38 citation statements)

References 43 publications

(95 reference statements)

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“…Soft short circuiting is a phenomenon where the magnesium deposit is partially passivated and slowly grows through the separator, eventually making contact with the counter electrode, therefore short circuiting the cell. This has been observed with Mg(TFSI) 2 electrolytes, which are unstable in the presence of magnesium metal (Ding et al, 2018; Kang et al, 2019).…”

Section: Resultsmentioning

confidence: 66%

“…Although magnesium is less likely to form dendrites compared to lithium, dendritic magnesium deposits been observed with both complex and simple salt electrolytes (Ding et al, 2018; Davidson et al, 2019). In particular, Mg(TFSI) 2 systems were found to short circuit cells due to the formation of an unstable solid electrolyte interphase (SEI), resultant from the partial decomposition of Mg(TFSI) 2 (Ding et al, 2018; Kang et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

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The Influence of Interfacial Chemistry on Magnesium Electrodeposition in Non-nucleophilic Electrolytes Using Sulfone-Ether Mixtures

Merrill

Schaefer

2019

Front. Chem.

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One of the limiting factors in the development of magnesium batteries is the reversibility of magnesium electrodeposition and dissolution at the anode. Often irreversibility is related to impurities and decomposition. Herein we report on the cycling behavior of magnesium metal anodes in different electrolytes, Mg(HMDS) 2 – 4 MgCl 2 in tetrahydrofuran (THF) and a butyl sulfone/THF mixture. The deposition morphology and anode-electrolyte interface is studied and related to Mg/Mg cell cycling performance. It is found that adding the sulfone caused the formation of a boundary layer at the electrode-electrolyte interface, which, in turn, resulted in a particle-like deposition morphology. This type of deposition has a high surface area, which alters the effective local current density and results in electronically isolated deposits. Extended cycling resulted in magnesium growth through a separator. Electrolyte decomposition is observed with and without the addition of the sulfone, however the addition of the sulfone increased the degree of decomposition.

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Section: Resultsmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 99%

The Influence of Interfacial Chemistry on Magnesium Electrodeposition in Non-nucleophilic Electrolytes Using Sulfone-Ether Mixtures

Merrill

Schaefer

2019

Front. Chem.

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“…In the Mg 2p spectra, there are two peaks detected at 49.5 and 51 eV, which correspond to metallic Mg 0 and oxidized Mg 2+ species (MgO, MgF 2 , and so forth), respectively. 30,31 Comparison of the intensities of these two features demonstrates that Mg 2+ species were dominant on the surface, indicating that MgO and MgF 2 are major components of the SEI. Since bulk MgO and MgF 2 suffer from a high Mg 2+ migration energy barrier, the interphase layer is likely to have a porous structure that allows Mg transport.…”

Section: Results Andmentioning

confidence: 99%

Establishing a Stable Anode–Electrolyte Interface in Mg Batteries by Electrolyte Additive

Diemant

Meng

et al. 2021

ACS Appl. Mater. Interfaces

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Simple magnesium salts with high electrochemical and chemical stability and adequate ionic conductivity represent a new-generation electrolyte for magnesium (Mg) batteries. Similar to other Mg electrolytes, the simple-salt electrolyte also suffers from high charge-transfer resistance on the Mg surface due to the adsorbed species in the solution. In the current study, we built a model Mg cell system with the Mg[B(hfip) 4 ] 2 /DME electrolyte and Chevrel phase Mo 6 S 8 cathode, to demonstrate the effect of such anode−electrolyte interfacial properties on the full-cell performance. It was found that the cell required additional activation cycles to achieve its maximal capacity. The activation process is mainly attributed to the conditioning of the anode−electrolyte interface, which could be boosted by introducing an additive amount of Mg(BH 4 ) 2 to the Mg[B(hfip) 4 ] 2 /DME electrolyte. Electrochemical and spectroscopic analyses revealed that the Mg(BH 4 ) 2 additive helps to remove the native oxide layer and promotes the formation of a solid electrolyte interphase layer on Mg. As a result, the full cell with the additive-containing electrolyte delivered a stable capacity from the second cycle onward. Further battery tests showed a reversible cycling for 600 cycles and an excellent rate capability, indicating good compatibility of the Mg(BH 4 ) 2 additive. The current study not only provides fundamental insights into the interfacial phenomena in Mg batteries but also highlights the facile tunability of the simple-salt Mg electrolytes.

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“…Chloride ions also react with corrosion products Mg (OH) 2 on the surfaces to materialize soluble MgCl 2 , which leads to more intense decomposition reactions of the alloys. [30,31] Furthermore, chloride ions adsorbed on the surfaces can reduce corrosion potentials of the alloys; thus, samples are more prone to corrosion and decomposition.…”

Section: Immersion Corrosion Experiments Of Mg-xzn-zr Alloysmentioning

confidence: 99%

Corrosion decomposition and mechanical behaviors of As‐cast Mg–xZn–Zr alloys

Zhou

Tian

et al. 2020

Materials & Corrosion

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Developing new‐type alloy materials with excellent decomposition properties and mechanical behaviors is a thorny issue for preparing fracturing balls in oil exploitation. As‐cast Mg–xZn–Zr alloys designed by regulating Zn contents have been fabricated in this study. Compressive strength and immersion corrosion test have been investigated to assess their feasibility as decomposition materials. Scanning electron microscopy and X‐ray diffract meter have also been used to characterize surface morphologies and phase structures for determining their decomposition mechanism. Results show that matrix phases and secondary phases with discontinuous reticular features form on the alloys. They also achieve excellent mechanical properties to ensure stability and pressure‐maintaining capacity in the decomposition process in chloride environment. Meanwhile, with Zn content and immersion time increasing, galvanic corrosion effect strengthens leading to accelerated specific mass loss rates of the alloys. Rapid corrosion decomposition of the alloys mainly attributes to anodic dissolution of matrix phases, exfoliation of microparticles, and poor resistance of corrosion products to the decomposition process. This study provides positive insight into the preparation of new‐type Mg alloys for guaranteeing fast decomposition of fracturing balls and also ensuring their compressive strength stability.

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Electrolyte Additive Enabling Conditioning-Free Electrolytes for Magnesium Batteries

Cited by 45 publications

References 43 publications

The Influence of Interfacial Chemistry on Magnesium Electrodeposition in Non-nucleophilic Electrolytes Using Sulfone-Ether Mixtures

The Influence of Interfacial Chemistry on Magnesium Electrodeposition in Non-nucleophilic Electrolytes Using Sulfone-Ether Mixtures

Establishing a Stable Anode–Electrolyte Interface in Mg Batteries by Electrolyte Additive

Corrosion decomposition and mechanical behaviors of As‐cast Mg–xZn–Zr alloys

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