Corrosion of magnesium electrolytes: chlorides – the culprit

Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G.; Zajíček, Jaroslav; Allred, Gary D.; Boggess, Bill

doi:10.1039/c2ee23686a

Cited by 211 publications

(222 citation statements)

References 24 publications

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Section: Resultssupporting

confidence: 51%

“…The anodic currents below the decomposition potential of the electrolyte on Pt working electrodes have been reported for Mg electrolytes with similar composition before and were attributed to pitting corrosion of the current collectors. 8,9,11,12 This observation was confirmed by investigation of the current collectors after the polarization by SEM, showing that the surface of the current collectors were covered with corrosion pits which is shown exemplarily for a Ni current collector in Figure 1b.Motivated by previous reports of high anodic stability of Grignard based electrolytes on glassy carbon and carbon coated Ti working electrodes, 9 the corrosion resistance of carbonaceous surfaces was investigated by linear sweep voltammetry and chronoamperometry.As shown in Figure 2a, a high anodic stability beyond 3 V was observed for a graphite current collector in linear sweep voltammetry. During chronoamperometry at a potential of 2.5 V vs. Mg/Mg 2+ no increase of the current density was measured during 48 h, confirming the good stability of the graphite current collector in the electrolyte.…”

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confidence: 51%

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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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Section: Resultssupporting

confidence: 51%

supporting

confidence: 51%

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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“…18 4 The cyclic voltammetry measurement is further conducted using a two-electrode coin cell with a Cu foil as the working electrode and a Mg ribbon as the counter electrode. The Cu electrode in the coin cell is stable below 1.7 V vs. Mg, and an increase in anodic current (about 0.3 mA cm −2 ) is observed above 1.78 V vs. Mg, as shown in the inset of Fig.…”

Section: Resultsmentioning

confidence: 99%

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Zeng

Wang

Yang

et al. 2017

J. Electrochem. Soc.

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We report the potential feasibility of a high-capacity and low-cost sulfur cathode that is compatible with nucleophilic electrolytes for Mg/S batteries. The electrochemical performance of sulfur in an easily prepared (PhMgCl) 2 -AlCl 3 /THF nucleophilic electrolyte depends on cathode current collectors. A sulfur cathode that uses Cu as a current collector, which is electrochemically stable in the range of operating voltage, exhibits an initial discharge capacity approximately corresponding to 659 mAh g −1 , and maintains a reversible capacity of 113 mAh g −1 after 20 cycles at a current density of 10 mA g −1 . It is different from the sulfur cathode with few capacities that uses stainless-steel as a current collector. Copper sulfides formed when sulfur is coated on a Cu current collector at 50 • C provide a strong chemical interaction between Cu and sulfur, which protects sulfur and increases its compatibility with the electrolyte. A metal-stabilized sulfur cathode provides an effective approach to improve the electrochemical performance of Mg/S batteries in nucleophilic electrolytes. There is a constant increase in the demand for low-cost, highenergy-density rechargeable batteries that utilize environmentally friendly elements for applications, such as market-competitive electric vehicles and large-scale power storage systems due to fossil energy shortage and environmental issues. Following the rapid development of electric vehicles with space available to mount battery packs, it is now necessary for batteries to possess good safety characteristics 1 and high volumetric energy density, which is more important than gravimetric energy density.2 Rechargeable magnesium batteries with magnesium as the anode may correspond to superior candidates compatible with post Li-ion batteries that contain a lithium metal anode, which provides a volumetric capacity (2062 mAh cm −3 ) exceeding that of a current graphite anode (777 mAh cm −3 ), 2 due to a relatively lower price ($2700 and $64800/ton for Mg and Li, respectively), 2,3 a higher theoretical volumetric capacity (3832 mAh cm −3 ), 2 and higher expected safety (the dendritic morphologies for magnesium deposits are lower than that for lithium). 4 Muldoon et al. first suggested an electrophilic sulfur cathode candidate with a high theoretical capacity (1671 mAh g −1 or 3459 mAh cm −3 ) corresponding to a conversion class as opposed to an insertion class. It is chemically incompatible with nucleophilic magnesium organohaloaluminate electrolytes and compatible with a non-nucleophilic electrolyte based on a recrystallized Mg complex [Mg 2 (μ-Cl) 3 (THF) 6 ][HMDSAlCl 3 ] formed from a reaction between hexamethyldisilazide magnesium chloride (HMDSMgCl) and AlCl 3 (3:1 molar ratio) in tetrahydrofuran (THF).2,4 The magnesium/sulfur (Mg/S) batteries yield a theoretical volumetric energy density exceeding 4000 Wh L −1 as compared to 2800 Wh L −1 for lithium/sulfur (Li/S) batteries.5 However, on cycling, Mg/S batteries also suffer from capacity fading, which results from low active...

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“…[15][16][17][18] However, these electrolytes may corrode non-inert current collectors at lower anodic potentials duo to the presence of halides in the cation and anion components of the electrolytes, although some of these electrolytes have shown impressive stability against electrochemical oxidation. 19 Hence, it is still necessary to find electrolytes with high stabilities on non-inert current collectors for a practical rechargeable Mg battery system. Nelson et al showed that decreasing the chloride content in Mg electrolytes by switching the Lewis acid from AlCl 3 to Al(OPh) 3 greatly improves the anodic stability up to 5 V on both Pt and stainless steel electrodes.…”

mentioning

confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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The electrolytes containing halide-free inorganic magnesium salt Mg(BH 4 ) 2 dissolved in ether solvents have shown reversible Mg deposition-dissolution performance. Herein, we improved the anodic stability of the electrolytes on non-inert stainless-steel electrode by mixing PP 14 TFSI ionic liquid with tetraglyme (TG) and dimethoxyethane (DME) ether solvents. The effect of mixing ratios and salt concentrations on the electrochemical behavior of the electrolyte were investigated. High anodic stability, good ionic conductivity, excellent cycling efficiency, feasibility of the preparation and good compatibility toward Mo 6 S 8 and TiO 2 insertion cathode make the electrolytes promising for the potential application in rechargeable magnesium batteries. 3-5 The development of magnesium electrolytes is considered as the most important challenge for the commercial application of rechargeable magnesium batteries because electrolyte properties govern battery performance and determine the class of cathodes to be utilized. 6 The significant progress is the reports of 0.25 mol L −1 Mg(AlCl 2 BuEt) 2 /THF (Bu=butyl, Et=ethyl) electrolyte 7,8 and 0.4 mol L −1 (PhMgCl) 2 -AlCl 3 /THF electrolyte, 9,10 which have high anodic stability (2.5 V and 3.3 V vs. Mg RE on inert Pt electrode, respectively) and reversibility of Mg deposition-dissolution. Recently, a family of novel boron based electrolytes with high ionic conductivity, excellent Mg deposition reversibility as well as high anodic potential were proposed.11,12 On the other hand, phenolate-based 13 and alkoxide-based 14 electrolytes exhibit air insensitive character and excellent magnesium depositiondissolution performance. Meanwhile, inorganic magnesium salt solutions synthesized by the acid-base reaction of MgCl 2 and Lewis acidic compounds such as AlCl 3 show high coulombic efficiency, low overpotential for magnesium deposition-dissolution and good anodic stability. [15][16][17][18] However, these electrolytes may corrode non-inert current collectors at lower anodic potentials duo to the presence of halides in the cation and anion components of the electrolytes, although some of these electrolytes have shown impressive stability against electrochemical oxidation.19 Hence, it is still necessary to find electrolytes with high stabilities on non-inert current collectors for a practical rechargeable Mg battery system. Nelson et al. showed that decreasing the chloride content in Mg electrolytes by switching the Lewis acid from AlCl 3 to Al(OPh) 3 greatly improves the anodic stability up to 5 V on both Pt and stainless steel electrodes.20 Ha et al. proposed a new class of electrolytes based on magnesium (II) bis(trifluoromethane sulfonyl)imide (Mg[N-(SO 2 CF 3 ) 2 ] 2 , Mg(TFSI) 2 ) dissolved in glymebased solvents with unique characteristics such as highly reduced corrosive nature toward the current collector, low volatility, high solvating power, and the ability to form an appropriate solvation sheath structure for Mg deposition-dissolution. 21 Recently, a whole new promisi...

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Corrosion of magnesium electrolytes: chlorides – the culprit

Cited by 211 publications

References 24 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

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

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