Divalent <i>closo</i>-monocarborane solvates for solid-state ionic conductors

Berger, Amanda; Ibrahim, Ainee; Buckley, Craig E.; Paskevicius, Mark

doi:10.1039/d2cp05583j

Cited by 7 publications

(13 citation statements)

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“…Considering all water molecules surrounding metal atoms in a range of 2.6 Å, the values of x = {4, 5, 6, and 7} have been observed along ion migration. x = 6 and 5 are present along 62 and 34%, respectively, of the dynamics, in good agreement with previous NMR observations . The mention in this paragraph indicates that ion diffusion on CTCHs is notably complex.…”

Section: Cation Diffusion Of Divalent Ctchssupporting

confidence: 91%

“…The completed details of the computational methods are shown in the Supporting Information and refs and . The obtained local environments of metal ions are in agreement with X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) measurements . As observed in Figures c and S1–S11, Mg- and Zn-CTCHs were obtained for n = {0, 2, 3, 4, 6, 7, 8, 9, 10, and 12}.…”

Section: Structures Of Divalent Ctchssupporting

confidence: 77%

“…The obtained local environments of metal ions are in agreement with X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) measurements. 53 As observed in Figures 2c and S1…”

Section: Structures Of Divalent Ctchssupporting

confidence: 66%

“…Interestingly, our calculations can verify the current hypothesis of the hydration effects on CTCHs. Under operando conditions, the 1 H NMR spectrum cannot distinguish non-coordinated or coordinated water molecules, which indicates rapid metal ion motion due to fast water exchange and B 12 H 12 anion rotation . In addition, CTCHs present symmetric plating/striping galvanostatically cycles for more than 100 h, which suggests a reversible diffusion mechanism .…”

Section: Cation Diffusion Of Divalent Ctchsmentioning

confidence: 96%

“…Under operando conditions, the 1 H NMR spectrum cannot distinguish non-coordinated or coordinated water molecules, which indicates rapid metal ion motion due to fast water exchange and B 12 H 12 anion rotation. 53 In addition, CTCHs present symmetric plating/striping galvanostatically cycles for more than 100 h, which suggests a reversible diffusion mechanism. 28 Here, first-principle MetaD simulations in addition to the AIMD for MgB 12 H 12 •12H 2 O were able to capture an intense water exchange during ion diffusion (Figure S14).…”

Section: Cation Diffusion Of Divalent Ctchsmentioning

confidence: 97%

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Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

et al. 2023

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The need for next-generation batteries is as urgent as ever. Over the past few decades, many attempts to find "beyond lithium" battery electrolytes have been reported, and, in particular, divalent closo-type complex hydride (CTCH) electrolytes are valuable alternatives to overcome the safety and energy density limitations of lithium-ion technology. Experiments have found that adding neutral molecules into the CTCH lattice can significantly promote its performance as battery electrolytes by accelerating cation conductivity (i.e., diffusion rate). However, the extremely high structural complexity of neutral molecules containing CTCHs hampers the exploration of ionic diffusion mechanisms and the design of high-performance batteries. To address this challenge, herein, cation diffusions of various CTCHs are analyzed by a workflow combining (i) a global optimization strategy based on a genetic algorithm, which will allow for identifying stable crystal phases of CTCHs, and (ii) ab initio kinetics and molecular dynamics simulations for cation diffusion. Without relying on any experimental information beforehand, this integrated strategy not only successfully predicts structural information that is comparable to experiments but also predicts almost identical diffusion activation energies compared to experimental observations. Based on these results, we developed robust structure-performance relationships that can precisely predict the divalent CTCH performance and identify the key factors that affect ionic conductivity. This study paves a new avenue for building a precise structure−performance picture of complex materials starting from near-zero information.

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Section: Cation Diffusion Of Divalent Ctchssupporting

confidence: 91%

Section: Structures Of Divalent Ctchssupporting

confidence: 77%

“…The obtained local environments of metal ions are in agreement with X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) measurements. 53 As observed in Figures 2c and S1…”

Section: Structures Of Divalent Ctchssupporting

confidence: 66%

Section: Cation Diffusion Of Divalent Ctchsmentioning

confidence: 96%

Section: Cation Diffusion Of Divalent Ctchsmentioning

confidence: 97%

See 3 more Smart Citations

Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

et al. 2023

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Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Sharma

Thomas

Gupta

2023

Batteries & Supercaps

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Calcium‐ion batteries (CIBs) are promising energy storage systems, but the unavailability of adept electrolytes has hindered their development. In this work, a range of silaborane clusters ( normalSnormalinormalBn-1Hn- ${{{\rm S}{\rm i}{\rm B}}_{n-1}{{\rm H}}_{n}^{-}}$ ; n=5–15) were investigated using density functional theory (DFT) at ωB97XD3/6‐311+G(d,p) level of theory. The vertical detachment energy (VDE), electrochemical stability window (ESW) and binding energy (BE) of the silaboranes were computed at the same level of DFT. A methodology based on molecular electrostatic potential surface analysis was designed to locate the most suitable binding site for calcium ions on the clusters. DFT results show that the SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ cluster turns out to be superior to other candidates. Effect of substitution on silaboranes ( normalSnormalinormalBn-1Hn-1 ${{{\rm S}{\rm i}{\rm B}}_{n-1}{{\rm H}}_{n-1}}$ R− R=−CH3, −NCS, −CF3, −F and −Cl) was computed. −NCS and −CF3 substituted SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ ions were found to be the best from DFT. Ab initio molecular dynamics (AIMD) studies were performed to explore the interactions between silaborane‐based electrolytes and the Ca anode. AIMD results highlight the decomposition of −NCS and −CF3 substituted SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ on Ca anode. DFT and AIMD studies reveal that −CH3 substituted silaborane‐based Ca‐salt (Ca(SiB11H11CH3)2) is the promising electrolyte for CIBs.

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Electrode materials for calcium batteries: Future directions and perspectives

Masese,

Kanyolo

2024

EcoEnergy

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Despite the prevailing dominance of lithium‐ion batteries in consumer electronics and electric vehicle markets, the growing apprehension over lithium availability has ignited a quest for alternative high‐energy‐density electrochemical energy storage systems. Rechargeable batteries featuring calcium (Ca) metal as negative electrodes (anodes) present compelling prospects, promising notable advantages in energy density, cost‐effectiveness, and safety. However, unlocking the full potential of rechargeable Ca metal batteries particularly hinges upon the strategic identification or design of high‐energy‐density positive electrode (cathode) materials. This imperative task demands expeditious synthetic routes tailored for their meticulous design. In this Perspective, we mainly highlight the development in the cathode materials for calcium batteries and accentuate the unparalleled promise of solid‐state metathesis routes in designing a diverse array of high‐performance electrode materials.

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Divalent closo-monocarborane solvates for solid-state ionic conductors

Abstract: Li-ion batteries have held the dominant position in battery research for the last 30+ years. However, due to inadequate resources and the cost of necessary elements (e.g., lithium ore) in...

Cited by 7 publications

References 84 publications

Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Electrode materials for calcium batteries: Future directions and perspectives

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Divalent closo-monocarborane solvates for solid-state ionic conductors

Abstract: Li-ion batteries have held the dominant position in battery research for the last 30+ years. However, due to inadequate resources and the cost of necessary elements (e.g., lithium ore) in...

Cited by 7 publications

References 84 publications

Explore the Ionic Conductivity Trends on B12H12 Divalent Closo-Type Complex Hydride Electrolytes

Explore the Ionic Conductivity Trends on B12H12 Divalent Closo-Type Complex Hydride Electrolytes

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB11H11CH3)2 as the Promising Electrolyte for Calcium‐Ion Batteries

Electrode materials for calcium batteries: Future directions and perspectives

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Product

Resources

About

Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

Explore the Ionic Conductivity Trends on B₁₂H₁₂ Divalent Closo-Type Complex Hydride Electrolytes

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries