Oxygen vacancies boosted fast Mg2+ migration in solids at room temperature

Wang, Qian; Li, Hongjiao; Zhang, Ruixue; Liu, Zhenzhen; Deng, Han‐Yu; Cen, Wanglai; Yan, Yigang; Chen, Yungui

doi:10.1016/j.ensm.2022.07.012

Cited by 28 publications

(25 citation statements)

References 43 publications

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“…Similarly, the addition of metal oxides to Mg[BH 4 ] 2 ·1.5NH 3 , including MgO and TiO 2 , increases ionic conductivity at 25 °C (∼10 −5 –10 −6 S cm −1 for Mg[BH 4 ] 2 ·1.5NH 3 @MgO and 3 × 10 −4 S cm −1 for Mg[BH 4 ] 2 ·1.5NH 3 + 60 wt% TiO 2 ). 79,80 Multiple theories exist to explain the increased ionic conductivity due to the formation of nanocomposites. For Mg[BH 4 ] 2 ·1.6NH 3 the addition of 75 wt% of MgO stabilises an amorphous phase, which increases the ionic conductivity.…”

Section: Resultsmentioning

confidence: 99%

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Divalent closo-monocarborane solvates for solid-state ionic conductors

Berger

Ibrahim

Buckley

et al. 2023

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 99%

“…80 Alternatively, TiO 2 addition to Mg[BH 4 ] 2 ·1.5NH 3 was theorised to increase the ionic conductivity due to increased oxygen vacancies on the surface of the metal oxide. 79…”

Section: Resultsmentioning

confidence: 99%

Divalent closo-monocarborane solvates for solid-state ionic conductors

Berger

Ibrahim

Buckley

et al. 2023

Phys. Chem. Chem. Phys.

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“…Additionally, it has been shown that composite materials allow for even higher ionic conductivities, and a high Mg 2+ conductivity, σ(Mg 2+ ) = 3.5 × 10 –4 S cm –1 , is obtained at 50 °C for the composite 0.4Mg(BH 4 ) 2 ·NH 3 – 0.6Mg(BH 4 ) 2 ·2NH 3 . This composite forms a eutectic melt at T > 55 °C, and this highly dynamical state can be stabilized with, e.g., MgO and Al 2 O 3 nanoparticles to form a solid, reaching a conductivity of up to σ(Mg 2+ ) ∼ 10 –5 S cm –1 at room temperature. − …”

Section: Introductionmentioning

confidence: 99%

Methylamine Magnesium Borohydrides as Electrolytes for All-Solid-State Magnesium Batteries

2023

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Solid-state magnesium electrolytes may pave the way for novel types of rechargeable, sustainable, and cheap batteries with high volumetric and gravimetric capacities. There are, however, currently no solid-state magnesium electrolytes that fulfill the requirements for solid-state battery applications. Here, we present the synthesis, structure, and properties of six new methylamine magnesium borohydride compounds, α- and β-Mg(BH4)2·6CH3NH2, Mg(BH4)2·3CH3NH2, and α-, α′- and β-Mg(BH4)2·CH3NH2. The β-Mg(BH4)2·CH3NH2 polymorph displays a record high Mg2+ ionic conductivity of σ(Mg2+) = 1.50 × 10–4 S cm–1 at room temperature. The high Mg2+ conductivity of β-Mg(BH4)·CH3NH2 is facilitated by a one-dimensional chain-like structure interconnected by weak dihydrogen bonds and dispersion interactions, forming a migration pathway across the chains. The oxidative stability of Mg(BH4)2·CH3NH2 is ∼1.2 V vs Mg/Mg2+, and the reversible plating and stripping were confirmed by cyclic voltammetry and symmetric cell cycling, revealing high stability toward magnesium electrodes for at least 50 cycles at 60 °C.

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“…[53][54][55][56] However, rechargeable batteries fabricated using Mg 2+ -, Ca 2+ -, and Zn 2+ -containing materials require higher ionic conductivities. Additionally, borohydride-based complex hydrides exhibit narrow voltage windows (<1.5 V), [57][58][59] as borohydride anions exhibit low oxidative stabilities originating from their low highest occupied molecular orbital levels. 60 Thus, in addition increasing ionic conductivity, one should replace the borohydride anion in complex hydride-based solid electrolytes with more oxidatively stable anions for practical battery applications.…”

Section: Introductionmentioning

confidence: 99%