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

Merrill, Laura; Schaefer, Jennifer L.

doi:10.3389/fchem.2019.00194

Cited by 24 publications

(17 citation statements)

References 27 publications

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“…Some work has also demonstrated that cycling Mg metal in this electrolyte can cause dendrite growth (Ding et al, 2018), although the deposits are not long and branch-like and have other formation characteristics that are different from dendrites. However, it is now more well-known that spherical Mg deposits can grow through separators and create soft-shorts in many different Mg electrolytes (Yoo et al, 2017;Merrill and Schaefer, 2019;Eaves-Rathert et al, 2020;Song et al, 2020). Results in the current work support the observation that soft-shorting is the origin of the overpotential decrease in Mg-Mg symmetric cells.…”

Section: Introductionsupporting

confidence: 83%

“…This characteristic of the symmetric cells is being discussed in the literature-some researchers initially said that a sharp overpotential decrease may be due to stabilization of the interface, not necessarily shorting (Tutusaus et al, 2017). However, more recent studies have demonstrated Mg growth through separators indicating clearer soft-shorting phenomena (Yoo et al, 2017;Merrill and Schaefer, 2019;Eaves-Rathert et al, 2020;Song et al, 2020). For the samples here, we also believe that a soft-short may have occurred as pieces of the glass fiber separator can be seen attached to deposits in Figure 5B.…”

Section: Discussionsupporting

confidence: 60%

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Al2O3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

et al. 2021

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Among the many emerging technologies under investigation as alternatives to the successful Lithium-ion battery, the magnesium battery is promising due to the wide availability of magnesium, its high volumetric capacity, and the possibility for safety improvements. One of the largest challenges facing rechargeable magnesium batteries is the formation of a passivation layer at the Mg metal anode interface when reactive species in the electrolyte are reduced at the electrode-electrolyte interface. To control the solid electrolyte interphase in Lithium batteries, protective layers called artificial solid electrolyte interphase (ASEI) layers have been successful in improving Li metal anode performance. The approach of protecting Mg metal anodes from electrolyte degradation has been demonstrated by fewer studies in the literature than Li systems. In this work, we discuss the properties of Al2O3 thin films deposited using atomic layer deposition as an artificial solid electrolyte interphase at the Mg anode. Our results demonstrate that Al2O3 does prevent electrolyte degradation due to the reductive nature of Mg. However, undesirable properties such as defects and layer breakdown lead to Mg growth that causes soft-shorting. The soft-shorting occurs with and without the protection layer, indicating the ALD layer does not prevent it and hinders Al2O3 from being an ideal candidate for a protection layer. Crucial effects of this layer on Mg electrochemistry at the interface were observed, including growth of Mg deposits leading to soft-shorting of the cell whose morphology showed a dependence on the Al2O3 layer. These results may provide guidelines for the future design and development of protective ASEI layers for Mg anodes.

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Section: Introductionsupporting

confidence: 83%

Section: Discussionsupporting

confidence: 60%

Al2O3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

et al. 2021

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“…It is well known that the blocking layers on the Mg anode formed via electrolyte decomposition or reaction with traces of water and oxygen prevent the diffusion of Mg 2+ ions; consequently, the reversible Mg deposition and dissolution are impeded . For instance, polar aprotic solvents including carbonates and nitriles, tend to form an impermeable layer on the metal surface, which limits the variety of the electrolyte . Surprisingly, compared to the number of studies carried out on different electrolyte systems and cathode materials, comparably few research groups dedicated their work to the anode material.…”

Section: Anode Materialsmentioning

confidence: 99%

Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges

Wang

Buchmeiser

2019

Adv Funct Materials

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abundant metal on earth. [19] In view of these merits and the high abundance of sulfur, increasing interest has been raised on post Li-S battery systems, including magnesium-selenium batteries, Mg-S batteries, which display higher energy density, low costs and improved safety in comparison to Li-S batteries. [11,[20][21][22][23] Despite the advantages of Mg-S batteries, major issues in this field are related to the severe overcharge behavior and low sulfur utilization of the cathode during charging and discharging in general, the formation of magnesium polysulfides and the slow diffusion of Mg 2+ , which all result in poor electrochemical behavior. [17,22,24,25] Substantial efforts have been made to improve cell performance so far, including the modification of cathode materials, anodes and separators, [25] the synthesis of novel electrolyte systems, [24,26] which all to some extent can improve the cell behavior. Figure 1d gives a timeline of all the novel findings in the area of Mg-S batteries in each year. Figure 1b demonstrates an overview of the topics addressed in the published research articles in Mg-S batteries. According to this survey, the research community developed a strong preference for investigating novel electrolyte systems, modifying sulfur cathode materials and carrying out mechanistic studies. By contrast, only few research groups devoted their work to the other components of a Mg-S battery, such as the anode and the separator. Major improvements related to the latter two will also be thoroughly discussed in the following sections.Several reviews already discussed the developments in Mg batteries based on intercalation cathode materials. [1,15,[27][28][29][30] By contrast, accounts on Mg batteries containing a sulfur-based conversion cathode, which benefits from high theoretical energy density, a reasonable potential difference with Mg, nontoxicity and high earth abundance [11,31,32] are rare. This review solely refers to Mg-S batteries that use sulfur-based conversion cathodes.The purposes of this review are to summarize and highlight the most up-to-date and novel findings for Mg-S batteries, addressing sulfur-based conversion cathodes and Mg anode materials, separator modifications as well as various electrolyte systems. Furthermore, since the research on Mg-S batteries is still at an initial stage, some challenges, including the capacity decay mechanism, a lack of suitable electrolyte systems and the passivation of the Mg anode, which so far impedes any superior electrochemical performance in Mg-S batteries, will also be addressed. In addition, we also listed and discussed some possible future prospects for high energy Mg-S batteries. Finally, the currently reported Mg-S systems have been summarized in a table for easy comparison.This review on rechargeable Mg-S batteries is arranged in the following sequences. In the first section, currently applied anode materials (various forms of Mg anodes) and prospective anodes are discussed. Next, various sulfur-based conversion cathodes, which mainly...

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“…A well‐deposited Mg layer with different morphology depending on the electrolyte formulation was observed by SEM (Figure a–c). The different surface morphology in each electrolyte indicated different Mg speciation . A compact agglomeration of particles that creates a Mg layer is shown in Figure a, a random Mg deposition is shown in Figure b, and nonhomogeneous distribution of Mg particles on a Cu electrode are shown in Figure c. It is clear that the preferred orientation of the deposited Mg during nucleation changes in different electrolytes.…”

Section: Resultsmentioning

confidence: 97%

Stripping and Plating a Magnesium Metal Anode in Bromide‐Based Non‐Nucleophilic Electrolytes

et al. 2020

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A non‐nucleophilic Hauser base hexamethyldisilazide (HMDS) magnesium electrolyte possesses inherent properties required for a magnesium–sulfur battery. However, the development of full cell batteries using HMDSCl‐based electrolytes is still hampered by a low coulombic efficiency. A new electrolyte formulation of non‐nucleophilic HMDS magnesium containing bromide as a halide instead of chloride was obtained through a simple and straightforward synthesis route. The electrochemistry of magnesium was investigated through plating and stripping in three different HMDSBr‐based electrolytes: Mg(HMDS)Br, Mg(HMDS)Br‐BEt3, and Mg(HMDS)Br‐AlEt3 dissolved in tetrahydrofuran. The different magnesium species present in the electrolytes were determined using NMR. Weak electron‐withdrawing Lewis acids, BEt3 and AlEt3 were used intentionally and their impact was investigated. Contrary to expectation, the substitution of chloride by bromide does not drastically narrow the electrochemical stability window. HMDSBr‐based electrolytes demonstrated long‐term (1000 cycles) stable reversibility and highly efficient (≈99 %) magnesium plating/tripping without a high ratio of bromide compared with the MgHMDSCl‐based electrolytes. The aprotic electrolyte shows comparatively high anodic stability (≈2.4 V vs. Mg/Mg2+) and high ionic conductivity of 1.16 mS cm−1 at room temperature. Plating of magnesium with low overpotential (<188 mV) revealed a morphology dependence on the electrolyte type with a shiny metallic homogenous layer, suggesting a rational balance between the nucleation and growth process in HMDSBr‐based electrolytes.

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

Cited by 24 publications

References 27 publications

Al2O3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Al2O3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges

Stripping and Plating a Magnesium Metal Anode in Bromide‐Based Non‐Nucleophilic Electrolytes

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