Monocarborane cluster as a stable fluorine-free calcium battery electrolyte

Kisu, Kazuaki; Kim, Sangryun; Shinohara, T.; Zhao, Kun; Züttel, Andreas; Orimo, Shin Ichi

doi:10.1038/s41598-021-86938-0

Cited by 60 publications

(64 citation statements)

References 52 publications

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“…[35] Similarly to the Mg case, the Ca(CB 11 H 12 ) 2 salt shows very limited solubility in G1 and THF, but dissolves readily in G1/THF mixtures producing electrolytes with high ionic conductivities, up to 4.0 mS cm -1 . [36] The Ca 2+ first solvation shell has not been determined, but likely both solvents participate, as for Mg 2+ .…”

Section: Electrolytes With Borohydrides and Other Boron-containing An...mentioning

confidence: 99%

Interfaces and Interphases in Ca and Mg Batteries

Forero-Saboya

Tchitchekova

Johansson

et al. 2021

Adv Materials Inter

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The development of high energy density battery technologies based on divalent metals as the negative electrode is very appealing. Ca and Mg are especially interesting choices due to their combination of low standard reduction potential and natural abundance. One particular problem stalling the technological development of these batteries is the low efficiency of plating/stripping at the negative electrode, which relates to several factors that have not yet been looked at systematically; the nature/concentration of the electrolyte, which determines the mass transport of electro‐active species (cation complexes) toward the electrode; the possible presence of passivation layers, which may hinder ionic transport and hence limit electrodeposition; and the mechanisms behind the charge transfer leading to nucleation/growth of the metal. Different electrolytes are investigated for Mg and Ca, with the presence/absence of chlorides in the formulation playing a crucial role in the cation desolvation. From a R&D point‐of‐view, proper characterization alongside modeling is crucial to understand the phenomena determining the mechanisms of the plating/stripping processes. The state‐of‐the‐art is here presented together with a short perspective on the influence of the cation solvation also on the positive electrode and finally an attempt to define guidelines for future research in the field.

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Section: Electrolytes With Borohydrides and Other Boron-containing An...mentioning

confidence: 99%

Interfaces and Interphases in Ca and Mg Batteries

Forero-Saboya

Tchitchekova

Johansson

et al. 2021

Adv Materials Inter

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“…Although they have the same charge (+2) of Mg 2+ and Ca 2+ , respective borohydrides are different in terms of conductivity, with solvated Mg(BH 4 ) 2 showing real promise as an electrolyte candidate with an oxidation stability of 1.2 V (by CV, cyclic voltammetry) ( Table 2 ) [ 272 , 275 , 276 ]. Recent trends in improving ionic conductivity have explored complexes with weaker coordinating ligands/counteranions, as is the case for CaB 12 H 12 [ 277 ]. Despite their low electrochemical stability, borohydrides give rise to rich speciation: nido- (typical tetrahydroborate BH 4 − ), planar- (B 6 H 6 6− ), and closo (B 10 H 10 2− ; B 12 H 12 2− ), making their alkali (Li + , Na + , K + ) and alkali-earth (Mg 2+ , Ca 2+ ) salts particularly appealing in ion conduction applications [ 278 , 279 , 280 , 281 ].…”

Section: Physical and Chemical Properties Of M(bh 4 ...mentioning

confidence: 99%

Complex Metal Borohydrides: From Laboratory Oddities to Prime Candidates in Energy Storage Applications

Comănescu

2022

Materials

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Despite being the lightest element in the periodic table, hydrogen poses many risks regarding its production, storage, and transport, but it is also the one element promising pollution-free energy for the planet, energy reliability, and sustainability. Development of such novel materials conveying a hydrogen source face stringent scrutiny from both a scientific and a safety point of view: they are required to have a high hydrogen wt.% storage capacity, must store hydrogen in a safe manner (i.e., by chemically binding it), and should exhibit controlled, and preferably rapid, absorption–desorption kinetics. Even the most advanced composites today face the difficult task of overcoming the harsh re-hydrogenation conditions (elevated temperature, high hydrogen pressure). Traditionally, the most utilized materials have been RMH (reactive metal hydrides) and complex metal borohydrides M(BH4)x (M: main group or transition metal; x: valence of M), often along with metal amides or various additives serving as catalysts (Pd2+, Ti4+ etc.). Through destabilization (kinetic or thermodynamic), M(BH4)x can effectively lower their dehydrogenation enthalpy, providing for a faster reaction occurring at a lower temperature onset. The present review summarizes the recent scientific results on various metal borohydrides, aiming to present the current state-of-the-art on such hydrogen storage materials, while trying to analyze the pros and cons of each material regarding its thermodynamic and kinetic behavior in hydrogenation studies.

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“…To overcome the poor anodic stability of early Mg(BH4) 2 -based electrolytes (1.7 V vs. Mg) (Mohtadi et al, 2012) (Carter et al, 2014;Tutusaus et al, 2015;Jay et al, 2019). Ca(CB 11 H 12 ) 2 was later adapted as one of few electrolytes to show room temperature reversible deposition of calcium (Kisu et al, 2021). Unfortunately, these unique carborane-type electrolytes present practical use issues as they can be some of the least cost-effective options and their syntheses cumbersome.…”

Section: Weakly Coordinating Anion Electrolytesmentioning

confidence: 99%

Solvation, Rational Design, and Interfaces: Development of Divalent Electrolytes

Leon

Liao

2022

Front. Energy Res.

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Rechargeable multivalent ion batteries are promising tools to complement current lithium-ion batteries for a future of diverse energy storage needs. Divalent Mg and Ca are attractive candidates for their high crustal abundance, high volumetric anode capacity, and infrequent dendrite formation during electrochemical cycling. Electrolyte research is central to these efforts and continually improves coulombic efficiencies towards the ideal 100%. This mini-review discusses recent work towards fundamental understandings that push these chemistries towards practical use. Piecing together compatible cathode and electrolytes for a complete practical multivalent ion battery lacks a cohesive method for further development and refinement. Understanding liquid solvation, utilizing rational design, and probing interfacial interactions are focal points that govern electrolyte performance. The combination of these areas will be critical for meaningful development.

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Monocarborane cluster as a stable fluorine-free calcium battery electrolyte

Cited by 60 publications

References 52 publications

Interfaces and Interphases in Ca and Mg Batteries

Interfaces and Interphases in Ca and Mg Batteries

Complex Metal Borohydrides: From Laboratory Oddities to Prime Candidates in Energy Storage Applications

Solvation, Rational Design, and Interfaces: Development of Divalent Electrolytes

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