Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries

Zhao‐Karger, Zhirong; Zhao, Xiangyu; Fuhr, Olaf; Fichtner, Maximilian

doi:10.1039/c3ra43206h

Cited by 175 publications

(212 citation statements)

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“…Anodic stabilities of electrolytes exceeding 3 V vs. Mg/Mg 2+ have been demonstrated recently. [5][6][7] However, until now all electrolytes for Mg batteries with good electrochemical performance (i.e. large voltage window, compatibility with metallic Mg and high ionic conductivity) contain chlorine, which was found to cause severe corrosion of current collectors made from Cu, Al, Ti and stainless steel.…”

mentioning

confidence: 99%

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

Wall

Zhao‐Karger

Fichtner

2014

ECS Electrochemistry Letters

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The compatibility of Ti, Cr, Ni, Fe, Al, steel type 304, Inconel 625, Hastelloy B and carbon coated current collectors with bisamide based electrolyte for Mg-batteries was investigated. Pitting corrosion of current collectors made from 3d-transition metals and steel type 304 was observed at potentials between 2.2-3.1 V vs. Mg/Mg 2+ . Anodic stability up to 3.8 V and resistance against corrosion for 48 h at a potential of 2.5 V vs. Mg/Mg 2+ and above was found for Inconel 625, Hastelloy B, graphite and carbon coated Al foil. © The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0111501eel] All rights reserved.Manuscript submitted October 9, 2014; revised manuscript received November 10, 2014. Published November 18, 2014 Recently Mg batteries have gained large interest due to the high theoretical energy density of Mg (2233 mAh g −1 and 3832 mAh cm −3 , respectively) but also because of the comparable low price, high abundance and the non-toxic properties of Mg.1,2 In contrast to metallic Li, no dendrite formation has been observed during electrochemical cycling of Mg.3,4 Thus, the technical application of metallic Mg anodes for secondary batteries with liquid electrolyte is not hampered by safety concerns as they exist for metallic Li. As the energy density of a battery is determined by the capacity of the electrode materials and by the potential difference between the anode and the cathode, both should be as high as possible. However, high operation potentials increase the driving force for oxidative decomposition of the electrolyte as well as for corrosion of the current collector at the cathode. Anodic stabilities of electrolytes exceeding 3 V vs. Mg/Mg 2+ have been demonstrated recently. [5][6][7] However, until now all electrolytes for Mg batteries with good electrochemical performance (i.e. large voltage window, compatibility with metallic Mg and high ionic conductivity) contain chlorine, which was found to cause severe corrosion of current collectors made from Cu, Al, Ti and stainless steel. 2,8,9Recently we developed a synthesis for bisamide based electrolytes with unprecedented anodic stability by reaction of magnesiumbis(hexamethyldisilazide) [(HMDS) 2 Mg] with AlCl 3 in different aprotic solvents, which are compatible with sulfur cathodes. 5,10 In order to utilize such electrolytes for magnesium batteries, we have now studied the corrosion behavior of various metals and steels and investigated if corrosion can be mitigated by a carbon coating. ExperimentalChronoamperometry and linear sweep voltammetry of current collectors was conducted vs. Mg foil, (Goodfellow, 99.99 %) in two...

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mentioning

confidence: 99%

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

Wall

Zhao‐Karger

Fichtner

2014

ECS Electrochemistry Letters

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“…10(a)]. Interestingly, the overcharging behavior is much less significant compared with the previous [29,32] 3.9 ∼2 ∼100 Yes 260@20/20 [32] 1000@71/30 [33] 236@20/50 [34] 800@167/20 [ [47,53] 3.1 [47] , 2.5 [53] 2 [47] , 8.5 [53] 99 Yes 70@17/20 [53] Mg(TFSI) 2 Prospective Article reports and an overpotential during charge and discharge was <0.4 V. The Mg-S cells were cycled for 30 times with capacity retention >86% [ Fig. 10(b)].…”

Section: Conductive Salt-based Electrolytesmentioning

confidence: 71%

“…[29] The in situ generated electrolytes in THF show an oxidative voltage of about 3.3 V, which is as good as the solution prepared by re-dissolving crystals. As this reaction can be conducted also in other solvents, higher stabilities are possible [ Fig.…”

Section: Non-nucleophilic Magnesium Electrolytes Hauser Base-based Elmentioning

confidence: 82%

“…With the more convenient approach using (HMDS) 2 Mg and AlCl 3 , [29] it was demonstrated that the Mg-S batteries with the bisamide-based electrolytes in glymes or binary glyme and ionic liquid considerably outperform those with previous Prospective Article electrolytes solution in THF. [32] As shown in Fig.…”

Section: Hexamethyldisilazide Electrolytesmentioning

confidence: 99%

“…This is the obvious reason for the superior electrochemical performance when compared with the electrolyte generated from HMDSMgCl-AlCl 3 containing several anionic species in form HMDS n AlCl 4−n − (n = 1-3). [28] Owing to the favorable electrochemical and chemical properties and its simplicity in preparation, this type of electrolyte has been employed in different Mg battery systems with both intercalation and conversion cathodes, including Mo 6 S 8 , [29] vanadium oxychloride (VOCl), [31] S, [32][33][34][35] Se, [36] and iodine. [37] Fluorinated alkoxide-based electrolytes…”

Section: Non-nucleophilic Magnesium Electrolytes Hauser Base-based Elmentioning

confidence: 99%

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Magnesium-sulfur battery: its beginning and recent progress

Zhao‐Karger

Fichtner

2017

MRS Communications

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Rechargeable magnesium (Mg) battery has been considered as a promising candidate for future battery generations because of its potential high-energy density, its safety features and low cost. The challenges lying ahead for the realization of Mg battery in general are to develop proper electrolytes fulfilling a multitude of requirements and to discover cathode materials enabling high-energy Mg batteries. The combination of Mg anode with a sulfur cathode is one of the promising electrochemical couples due to its advantages of safety, low costs, and a high theoretical energy density of over 3200 Wh/L. However, the research on magnesium-sulfur (Mg-S) battery is just at its beginning and the development of suitable electrolytes has been the key challenge for further improvement, and, thus, in the focus of recent research. In this review, we highlight the recent progress achieved in Mg electrolytes and Mg-S batteries and discuss the major technical issues, which must be resolved for the improvement of Mg-S batteries.

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Multivalent Metallic Anodes for Rechargeable Batteries

Schaefer

Merrill

2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Multivalent metals are an option for beyond lithium‐ion battery anodes due to their high relative abundance and/or charge capacities; of particular interest is the use of zinc, iron, magnesium, aluminum, and calcium metal. The state of the art and future directions of each metallic anode are discussed in terms of anode morphology, treatment, and electrolyte formulation. Zinc and iron anodes are reported in the context of aqueous electrolytes where anode morphology and carbon structure/loading have a great impact on battery performance. Magnesium, aluminum, and calcium, conversely, are discussed in the context of nonaqueous electrolytes, where electrolyte formulation is a determining factor in battery performance.

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Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries

Cited by 175 publications

References 19 publications

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

Magnesium-sulfur battery: its beginning and recent progress

Multivalent Metallic Anodes for Rechargeable Batteries

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