Cation reduction and comproportionation as novel strategies to produce high voltage, halide free, carborane based electrolytes for rechargeable Mg batteries

McArthur, Scott G.; Geng, Linxiao; Guo, Juchen; Lavallo, Vincent

doi:10.1039/c5qi00171d

Cited by 92 publications

(57 citation statements)

References 38 publications

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“…Simple Mg salts including Mg(TFSI) 2 and Mg (PF 6 ) 2 were confirmed as not working for reversible Mg deposition due to the instability of anions with Mg metal. [46,48] Magnesium carborane, [49][50][51] Magnesium hexafluoroisopropylaluminate, [52] Magnesium hexafluoroisopropylborate, [53][54][55] and Magnesium perfluorinated pinacolatoborate [56] salts were reported as rare examples of Cl-free non-corrosive electrolytes for reversible Mg deposition.…”

Section: Introductionmentioning

confidence: 99%

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries

Moss

Zhang

Nielson

et al. 2019

Batteries & Supercaps

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DFT calculations were conducted to provide unprecedented thermodynamic insights on tetrahydrofuran (THF) solvation, isomerization, and complexation of possible MgÀ Cl coordination species for popular MgÀ Cl electrolytes for magnesium batteries. Computational results using the M06-2x functional with the 6-31 + G(d) basis set indicate that trigonal bipyramidal e,e-cis-tbp-MgCl 2 (THF) 3 dichloride species and octahedral [MgCl (THF) 5 ] + monochloride species are the dominant mononuclear species. These two can combine to form the dinuclear species [(μ-Cl) 3 Mg 2 (THF) 6 ] + with a free energy À 6.30 kcal/mol, which is calculated to be the dominant MgÀ Cl species in solution. Two mono-cation species, [(μ-Cl) 3 Mg 2 (THF) 6 ] + and [MgCl(THF) 5 ] + , have comparable LUMO energies, thus both of them can act as active species for Mg deposition. However, the significant dominance of the dinuclear species in the electrolyte indicates that it is the primary species involved in reversible Mg deposition.[a] J.

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Section: Introductionmentioning

confidence: 99%

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries

Moss

Zhang

Nielson

et al. 2019

Batteries & Supercaps

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“…These electrolytes are usually corrosive and have much narrower electrochemical window compared with LIB electrolytes. Recent developments, particularly on all-phenyl-complex electrolytes, 38 all-inorganic electrolytes, 39À42 and nonhalide electrolytes, 43,44 have established electrolytes with significantly improved voltage windows and activities. The second major challenge is associated with the lack of high-voltage cathode materials that can provide good Mg 21 insertion/extraction kinetics.…”

Section: Introductionmentioning

confidence: 99%

Rechargeable Mg–Li hybrid batteries: status and challenges

et al. 2016

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“…It should be noted that by using ether‐based solvents with more donating ligands and the addition of LiBH 4 , as demonstrated by Mohtadi et al, Shao et al, Buttry et al, and Nuli et al, electrolytes based on simple Mg(BH 4 ) 2 show optimized electrochemical properties . Non‐nucleophilic boron clusters including (C 2 B 10 H 11 )MgCl, Mg(CB 11 H 12 ) 2 , and Mg(HCB 9 H 9 ) 2 , discovered by Mohtadi and co‐workers and Guo and co‐workers have also been demonstrated to show reversible Mg stripping/plating properties with much higher oxidative stability (3.6 V vs Mg) compared with Mg(BH 4 ) 2 electrolytes (Table ) . It is worth mentioning that 0.75 m Mg(CB 11 H 12 ) 2 electrolyte shows a fair ionic conductivity of 1.8 mS cm −1 , a wide electrochemical window (3.6 V vs Mg), and relatively high CE of >99%, as shown in Figure e.…”

Section: Recent Mg‐ion Electrolyte Advancesmentioning

confidence: 91%

Rechargeable Magnesium Batteries using Conversion‐Type Cathodes: A Perspective and Minireview

et al. 2018

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would impose restrictions on the penetration of LIBs into these large-volume markets. [3,4] In addition, after 25 years of continuous improvements, the mature LIBs technology is approaching a fundamental limit in terms of energy density (slightly above 300 W h kg −1 ) and costs at the materials level. [4][5][6] With the aforementioned concerns, alternative battery concepts have significantly stimulated research interests to further drive battery technologies to increase both the gravimetric and volumetric energy densities, reduce the cost, and expand the cycling life. [3,6,7] The "beyond Li-ion" technologies such as lithium-air, lithium-sulfur (Li-S), multivalent batteries, and solid-state batteries show the unique feature of using metal anodes that can store more energy via a reversible metal plating/stripping process. Unfortunately, these emerging or reviving technologies involving lithium metal inevitably meet the critical challenges of resource shortage. Furthermore, the high reactivity of lithium metal leads to electrolyte consumption and nonuniform lithium distribution (even dendritic growth) during cycling. These issues still hamper the mainstream commercialization of the lithium-metal-based batteries. [8,9] Rechargeable magnesium (Mg) batteries may offer considerable advantages (see Table 1) over Li-metal batteries because the metallic Mg anode shows double the volumetric capacity, safer and easier processing features, more uniform and nondendritic electroplating during cell charging, and cheaper costs due to its greater abundance in the earth crust. [4,[10][11][12][13] Based on these advantages, intensive attention has been garnered toward the development of new electrolytes, cathodes, and their corresponding mechanistic understandings for the rechargeable Mg batteries. Additionally, several industries including Pellion Technologies (a spin-off company from Massachusetts Institute of Technology), the Toyota Research Institute of North America, and recently Sony Corporation have initiated R&D projects for the rechargeable Mg batteries and tried to find practical application pathways. Nonetheless, developing a high-energy-density Mg battery with long cycle life and high rate capability is still a huge challenge due to the lack of high-performance cathodes and suitable Mg-ion electrolytes. [9,12] It is fair to state that the Chevrel phases, reported by Aurbach et al. in 2000, are still the most attractive Mg-ion Rechargeable magnesium (Mg) batteries are one of the potential contenders to replace current Li-ion batteries to power future electric vehicles with lower cost, higher safety, and extended mileage. To achieve this goal, both high-voltage intercalation-type cathodes and high-capacity conversion-type cathodes are considered. However, there are still no reports to compare rechargeable Mg batteries with the state-of-the art Li-ion batteries in terms of their overall performance. Also, potential cathode materials to deliver higher energy density in rechargeable Mg batteries are rarely summarized. Here, t...

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Cation reduction and comproportionation as novel strategies to produce high voltage, halide free, carborane based electrolytes for rechargeable Mg batteries

Abstract: The chemical reduction of reactive cations and comproportionation are two new strategies reported to produce halide free carborane based electrolytes for rechargeable Mg batteries.

Cited by 92 publications

References 38 publications

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries

Rechargeable Mg–Li hybrid batteries: status and challenges

Rechargeable Magnesium Batteries using Conversion‐Type Cathodes: A Perspective and Minireview

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