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Rechargeable Ca batteries offer the advantages of high energy density, low cost, and earth-abundant constituents, presenting a viable alternative to lithium-ion batteries. However, using polymer electrolytes in practical Ca batteries is not often reported, despite its potential to prevent leakage and preserve battery flexibility. Herein, a Ca(BH 4 ) 2 -based gel-polymer electrolyte (GPE) is prepared from Ca(BH 4 ) 2 and poly(tetrahydrofuran) (pTHF) and tested its performance in Ca batteries. The electrolyte demonstrates excellent stability against Ca-metal anodes and high ionic conductivity. The results of infrared spectroscopy and 1 H and 11 B NMR indicate that the terminal ─OH groups of pTHF reacted with BH 4 - anions to form B─H─(pTHF) 3 moieties, achieving cross-linking and solidification. Cyclic voltammetry measurements indicate the occurrence of reversible Ca plating/stripping. To improve the performance at high current densities, the GPE is supplemented with LiBH 4 to achieve a lower overpotential in the Ca plating/stripping process. An all-solid-state Ca-metal battery with a dual-cation (Ca 2+ and Li + ) GPE, a Ca-metal anode, and a Li 4 Ti 5 O 12 cathode sustained >200 cycles, confirming their feasibility. The results pave the way for further developing lithium salt-free Ca batteries by developing electrolyte salts with high oxidation stability and optimal electrochemical properties., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Solid-state methods for cooling and heating promise a sustainable alternative to current compression cycles of greenhouse gases and inefficient fuel-burning heaters. Barocaloric effects (BCE) driven by hydrostatic pressure (p) are especially encouraging in terms of large adiabatic temperature changes (|ΔT| ≈ 10 K) and isothermal entropy changes (|ΔS| ≈ 100 J K -1  kg -1 ). However, BCE typically require large pressure shifts due to irreversibility issues, and sizeable |ΔT| and |ΔS| seldom are realized in a same material. Here, the existence of colossal and reversible BCE in LiCB 11 H 12 is demonstrated near its order-disorder phase transition at ≈380 K. Specifically, for Δp ≈ 0.23 (0.10) GPa, |ΔS rev | = 280 (200) J K -1  kg -1 and |ΔT rev | = 32 (10) K are measured, which individually rival with state-of-the-art BCE figures. Furthermore, pressure shifts of the order of 0.1 GPa yield huge reversible barocaloric strengths of ≈2 J K -1  kg -1  MPa -1 . Molecular dynamics simulations are performed to quantify the role of lattice vibrations, molecular reorientations, and ion diffusion on the disclosed BCE. Interestingly, lattice vibrations are found to contribute the most to |ΔS| while the diffusion of lithium ions, despite adding up only slightly to the entropy change, is crucial in enabling the molecular order-disorder phase transition., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

The lithium-ion transport mechanism in 0.7Li(CB 9 H 10 )-0.3Li(CB 11 H 12 ) complex hydride solid electrolyte was studied over a wide time-scale (ns-ms) by choosing appropriate techniques for assessing ionic motion on the desired time-scale using nuclear magnetic resonance (NMR) relaxation, AC impedance, and pulsed field gradient-NMR (PFG-NMR) measurements. The 7 Li NMR line width decreased with increasing temperature, and the spin-lattice relaxation time T 1 for the cation and anions showed a minimum near 303 K, indicating that the lithium ions and the anions were highly mobile. The activation energy estimated from the analysis of the NMR relaxation time matched well with the values estimated from the AC impedance and PFG-NMR. This confirms that the lithium-ion motion in 0.7Li(CB 9 H 10 )-0.3Li(CB 11 H 12 ) is the same over a wide time-scale, suggesting steady Li-ion motion over a wide transport range. This understanding offers insights into strategies for designing complex hydride lithium superionic conductors.

Hierarchically porous carbon microlattices (HPCMLs) fabricated by using a composite photoresin and stereolithography (SLA) 3D printing is reported. Containing magnesium oxide nanoparticles (MgO NPs) as porogens and multilayer graphene nanosheets as UV-scattering inhibitors, the composite photoresin is formed to simple cubic microlattices with digitally designed porosity of 50%. After carbonization in vacuum at 1000 °C and chemical removal of MgO NPs, it is realized that carbon microlattices possessing hierarchical porosity are composed of the lattice architecture (≈100 µm), macropores (≈5 µm), mesopores (≈50 nm), and micropores (≈1 nm). The linear shrinkage after pyrolysis is as small as 33%. Compressive strength of 7.45 to 10.45 MPa and Young's modulus of 375 to 736 MPa are achieved, proving HPCMLs a robust mechanical component among reported carbon materials with a random pore structure. Having a few millimeters in thickness, the HPCMLs can serve as thick supercapacitor electrodes that demonstrate gravimetric capacitances 105 and 13.8 F g -1 in aqueous and organic electrolyte, reaching footprint areal capacitances beyond 10 and 1 F cm -2 , respectively. The results present that the composite photoresin for SLA can yield carbon microarchitectures that integrate structural and functional properties for structural energy storages ., (© 2023 Wiley-VCH GmbH.)

As potential alternatives to Li-ion batteries, rechargeable Ca metal batteries offer advantageous features such as high energy density, cost-effectiveness, and natural elemental abundance. However, challenges, such as Ca metal passivation by electrolytes and a lack of cathode materials with efficient Ca 2+ storage capabilities, impede the development of practical Ca metal batteries. To overcome these limitations, the applicability of a CuS cathode in Ca metal batteries and its electrochemical properties are verified herein. Ex situ spectroscopy and electron microscopy results show that a CuS cathode comprising nanoparticles that are well dispersed in a high-surface-area carbon matrix can serve as an effective cathode for Ca 2+ storage via the conversion reaction. This optimally functioning cathode is coupled with a tailored, weakly coordinating monocarborane-anion electrolyte, namely, Ca(CB 11 H 12 ) 2 in 1,2-dimethoxyethane/tetrahydrofuran, which enables reversible Ca plating/stripping at room temperature. The combination affords a Ca metal battery with a long cycle life of over 500 cycles and capacity retention of 92% based on the capacity of the 10th cycle. This study confirms the feasibility of the long-term operation of Ca metal anodes and can expedite the development of Ca metal batteries., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Topological data analysis based on persistent homology has been applied to the molecular dynamics simulation for the fast ion-conducting phase (α-phase) of AgI to show its effectiveness on the ion migration mechanism analysis. Time-averaged persistence diagrams of α-AgI, which quantitatively record the shape and size of the ring structures in the given atomic configurations, clearly showed the emergence of the four-membered rings formed by two Ag and two I ions at high temperatures. They were identified as common structures during the Ag ion migration. The averaged potential energy change due to the deformation of the four-membered ring during Ag migration agrees well with the activation energy calculated from the conductivity Arrhenius plot. The concerted motion of two Ag ions via the four-membered ring was also successfully extracted from molecular dynamics simulations by our approach, providing new insight into the specific mechanism of the concerted motion.

Boron-based two-dimensional (2D) materials are an excellent platform for nanoelectronics applications. Rhombohedral boron monosulfide (r-BS) is attracting particular attention because of its unique layered crystal structure suitable for exploring various functional properties originating in the 2D nature. However, studies to elucidate its fundamental electronic states have been largely limited because only tiny powdered crystals were available, hindering a precise investigation by spectroscopy such as angle-resolved photoemission spectroscopy (ARPES). Here we report the direct mapping of the band structure with a tiny (∼20 × 20 μm 2 ) r-BS powder crystal by utilizing microfocused ARPES. We found that r-BS is a p-type semiconductor with a band gap of >0.5 eV characterized by the anisotropic in-plane effective mass. The present results demonstrate the high applicability of micro-ARPES to tiny powder crystals and widen an opportunity to access the yet-unexplored electronic states of various novel materials.

Hydrogen can be stored in the interstitial sites of the lattices of intermetallic compounds. To date, intermetallic compound LaNi 5 or related LaNi 5 -based alloys are known to be practical hydrogen storage materials owing to their higher volumetric hydrogen densities, making them a compact hydrogen storage method and allowing stable reversible hydrogen absorption and desorption reactions to take place at room temperature below 1.0 MPa. By contrast, gravimetric hydrogen density is required for key improvements (e.g., gravimetric hydrogen density of LaNi 5 : 1.38 mass%). Although hydrogen storage materials have typically been evaluated for their hydrogen storage properties below 10 MPa, reactions between hydrogen and materials can be facilitated above 1 GPa because the chemical potential of hydrogen dramatically increases at a higher pressure. This indicates that high-pressure experiments above 1 GPa could clarify the latent hydrogen absorption reactions below 10 MPa and potentially explore new hydride phases. In this study, we investigated the hydrogen absorption reaction of LaNi 5 above 1 GPa at room temperature to understand their potential hydrogen storage capacities. The high-pressure experiments on LaNi 5 with and without an internal hydrogen source (BH 3 NH 3 ) were performed using a multi-anvil-type high-pressure apparatus, and the reactions were observed using in situ synchrotron radiation X-ray diffraction with an energy dispersive method. The results showed that 2.07 mass% hydrogen was absorbed by LaNi 5 at 6 GPa. Considering the unit cell volume expansion, the estimated hydrogen storage capacity could be 1.5 times higher than that obtained from hydrogen absorption reaction below 1.0 MPa at 303 K. Thus, 33% of the available interstitial sites in LaNi 5 remained unoccupied by hydrogen atoms under conventional conditions. Although the hydrogen-absorbed LaNi 5 H x (x < 9) was maintained below 573 K at 10 GPa, LaNi 5 H x began decomposing into NiH, and the formation of a new phase was observed at 873 K and 10 GPa. The new phase was indexed to a hexagonal or trigonal unit cell with a ≈ 4.44 Å and c ≈ 8.44 Å. Further, the newly-formed phase was speculated to be a new hydride phase because the Bragg peak positions and unit cell parameters were inconsistent with those reported for the La-Ni intermetallic compounds and La-Ni hydride phases.

High ionic conductivity, suitable mechanical strength, and electrochemical stability are the main requirements for high-performance poly(ethylene oxide)-based electrolytes. However, the low ionic conductivity owing to the crystallinity of the ethylene oxide chain that limits the discharge rate and low-temperature performance has restricted the development and commercialization of these electrolytes. Lithium electrolytes that combine high ionic conductivity with a high lithium transference number are rare and are essential for high-power batteries. Here, we report hexagonal arranged porous scaffolds for holding prototype polyethylene glycol-based composite electrolytes containing solvate ionic liquid. The appealing electrochemical and thermal properties indicate their potential as electrolytes for safer rechargeable lithium-ion batteries. The porous scaffolds in the composite electrolytes ensure better electrochemical performance towing to their shortened pores (sizes of 3-14 μm), interconnected pathways, and improved lithium mobility. We demonstrate that both molecular design and porous microstructures are essential for improving performance in polymer electrolytes., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

The use of hydrogen in iron and steel has the potential to improve mechanical properties via altering the phase stability and dislocation behavior. When hydrogen is introduced under several gigapascals, a stoichiometric composition of hydrogen can be introduced for steel compositions. In this study, a face-centered cubic (fcc) stainless steel was hydrogenated under several gigapascals. When the steel was not hydrogenated, the microstructure after depressurization was an fcc with a hexagonal close-packed (hcp) structure. In contrast, the hydrogenation treatment resulted in a fine lath body-centered cubic (bcc) structure arising from diffusionless transformation. In particular, the bcc phase formed through the following transformation sequence: fcc → hcp → dhcp (double hexagonal close-packed phase) → bcc. That is, the use of hydrogenation treatment realized fine microstructure evolution through a new type of diffusionless transformation sequence, which is expected to be used in future alloy design strategies for developing high-strength steels., (© 2021. The Author(s).)

Traditional refrigeration technologies based on compression cycles of greenhouse gases pose serious threats to the environment and cannot be downscaled to electronic device dimensions. Solid-state cooling exploits the thermal response of caloric materials to changes in the applied external fields (i.e., magnetic, electric and/or mechanical stress) and represents a promising alternative to current refrigeration methods. However, most of the caloric materials known to date present relatively small adiabatic temperature changes ([Formula: see text] to 10 K) and/or limiting irreversibility issues resulting from significant phase-transition hysteresis. Here, we predict by using molecular dynamics simulations the existence of colossal barocaloric effects induced by pressure (isothermal entropy changes of [Formula: see text] J K[Formula: see text] kg[Formula: see text]) in the energy material Li[Formula: see text]B[Formula: see text]H[Formula: see text]. Specifically, we estimate [Formula: see text] J K[Formula: see text] kg[Formula: see text] and [Formula: see text] K for a small pressure shift of P = 0.1 GPa at [Formula: see text] K. The disclosed colossal barocaloric effects are originated by a fairly reversible order-disorder phase transformation involving coexistence of Li[Formula: see text] diffusion and (BH)[Formula: see text] reorientational motion at high temperatures.

High-energy-density and low-cost calcium (Ca) batteries have been proposed as 'beyond-Li-ion' electrochemical energy storage devices. However, they have seen limited progress due to challenges associated with developing electrolytes showing reductive/oxidative stabilities and high ionic conductivities. This paper describes a calcium monocarborane cluster salt in a mixed solvent as a Ca-battery electrolyte with high anodic stability (up to 4 V vs. Ca 2+ /Ca), high ionic conductivity (4 mS cm -1 ), and high Coulombic efficiency for Ca plating/stripping at room temperature. The developed electrolyte is a promising candidate for use in room-temperature rechargeable Ca batteries.

The hydrogen storage properties and crystal structures of YMgNi 4 -based alloys, which were synthesized from (2 - x )YNi 2 and x MgNi 2 (0.6 ≤ x ≤ 1.2), were investigated by pressure-composition-temperature measurements and powder neutron diffraction at a deuterium gas pressure to understand the hydrogen absorption and desorption reactions viewed from atomic arrangements around H atoms. Reducing the amounts of MgNi 2 , which was utilized as a Mg source in YMgNi 4 -based alloys, has been observed to lower the hydrogen absorption and desorption pressures and increase the hydrogen storage capacities. However, the reversible hydrogen capacity attained a maximum value of 1.2 mass % at x = 0.8 because of the formation of a thermodynamically stable hydride in which hydrogen was not released at x = 0.6. In the case of x = 0.6, the presence of excessive Y atoms around the H atoms in the hydrogen-absorbed phase would lead to the formation of a hydride with stronger interaction between Y and H because of the affinity between them. Moreover, the presence of small amounts of D atoms with short interatomic D-D distances (1.6 and 1.9 Å) in the deuterium-absorbed phase (Y 0.81 Mg 1.19 Ni 4.00 D 3.35 and Y 1.06 Mg 0.94 Ni 4.00 D 3.86 ) at <5 MPa and 323 K was proposed by the crystal structural investigations. The D atoms with short D-D interatomic distances were located in the same local atomic arrangements of D atoms in a deuterium-absorbed phase, which were formed at a higher-pressure range, and had higher hydrogen storage capacities than the deuterium-absorbed phases in this study., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Geant4 Monte Carlo simulations were carried out to investigate the possible shielding materials of aluminum, polyethylene, hydrides, complex hydrides and composite materials for radiation protection in spacecraft by considering two physical parameters, stopping power and fragmentation cross section. The dose reduction with shielding materials was investigated for Fe ions with energies of 500 MeV/n, 1 GeV/n and 2 GeV/n which are around the peak of the GCR energy spectrum. Fe ions easily stop in materials such as polyethylene and hydrides as opposed to materials such as aluminum and complex hydrides including high Z metals with contain little or no hydrogen. Attenuation of the primary particles in the shielding and fragmentation into more lightly charged and therefore more penetrating secondary particles are competing factors: attenuation acts to reduce the dose behind shielding while fragmentation increases it. Among hydrogenous materials, 6 Li 10 BH 4 was one of the more effective shielding materials as a function of mass providing a 20% greater dose reduction compared to polyethylene. Composite materials such as carbon fiber reinforced plastic and SiC composite plastic offer 1.9 times the dose reduction compared to aluminum as well as high mechanical strength. Composite materials have been found to be promising for spacecraft shielding, where both mass and volume are constrained., Competing Interests: Declaration of Competing Interest The authors declare that there are no potential conflicts of interest., (Copyright © 2020 The Committee on Space Research (COSPAR). Published by Elsevier Ltd. All rights reserved.)

The properties of the mixed system LiBH 4 -LiCl-P 2 S 5 are studied with respect to all-solid-state batteries. The studied material undergoes an amorphization upon heating above 60 °C, accompanied with increased Li + conductivity beneficial for battery electrolyte applications. The measured ionic conductivity is ∼10 -3 S cm -1 at room temperature with an activation energy of 0.40(2) eV after amorphization. Structural analysis and characterization of the material suggest that BH 4 groups and PS 4 may belong to the same molecular structure, where Cl ions interplay to accommodate the structural unit. Thanks to its conductivity, ductility and electrochemical stability (up to 5 V, Au vs. Li + /Li), this new electrolyte is successfully tested in battery cells operated with a cathode material (layered TiS 2 , theo. capacity 239 mA h g -1 ) and Li anode resulting in 93% capacity retention (10 cycles) and notable cycling stability under the current density ∼12 mA g -1 (0.05C-rate) at 50 °C. Further advanced characterisation by means of operando synchrotron X-ray diffraction in transmission mode contributes explicitly to a better understanding of the (de)lithiation processes of solid-state battery electrodes operated at moderate temperatures.

Neutron powder diffraction profiles were collected for iron deuteride (FeD x ) while the temperature decreased from 1023 to 300 K for a pressure range of 4-6 gigapascal (GPa). The ε' deuteride with a double hexagonal close-packed (dhcp) structure, which coexisted with other stable or metastable deutrides at each temperature and pressure condition, formed solid solutions with a composition of FeD 0.68(1) at 673 K and 6.1 GPa and FeD 0.74(1) at 603 K and 4.8 GPa. Upon stepwise cooling to 300 K, the D-content x increased to a stoichiometric value of 1.0 to form monodeuteride FeD 1.0 . In the dhcp FeD 1.0 at 300 K and 4.2 GPa, dissolved D atoms fully occupied the octahedral interstitial sites, slightly displaced from the octahedral centers in the dhcp metal lattice, and the dhcp sequence of close-packed Fe planes contained hcp-stacking faults at 12%. Magnetic moments with 2.11 ± 0.06 μ B /Fe-atom aligned ferromagnetically in parallel on the Fe planes.

Hexagonal close-packed iron hydride, hcp FeH x , is absent from the conventional phase diagram of the Fe-H system, although hcp metallic Fe exists stably over extensive temperature (T) and pressure (P) conditions, including those corresponding to the Earth's inner core. In situ X-ray and neutron diffraction measurements at temperatures ranging from 298 to 1073 K and H pressures ranging from 4 to 7 GPa revealed that the hcp hydride was formed for FeH x compositions when x < 0.6. Hydrogen atoms occupied the octahedral interstitial sites of the host metal lattice both partially and randomly. The hcp hydride exhibited a H-induced volume expansion of 2.48(5) Å 3 /H-atom, which was larger than that of the face-centered cubic (fcc) hydride. The hcp hydride showed an increase in x with T, whereas the fcc hydride showed a corresponding decrease. The present study provides guidance for further investigations of the Fe-H system over an extensive x-T-P region.

The hydrogen-release reaction of a complex transition metal hydride, LaMg 2 NiH 7 , composed of La 3+ , 2×Mg 2+ , [NiH 4 ] 4- and 3×H - , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg 2 NiH 7 released hydrogen at approximately 567 K and decomposed into LaH 2-3 and Mg 2 Ni. Before the reaction, covalently bound hydrogen (H c ° v. ) in [NiH 4 ] 4- exhibited a larger atomic displacement than H - , although a weakening of the chemical bonds around [NiH 4 ] 4- and H - was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of H c ° v. that induces the hydrogen-release reaction rather than H - . As an isothermal reaction, LaMg 2 NiH 7 formed LaMg 2 NiH 2.4 at 503 K in vacuum for 48 h, and LaMg 2 NiH 2.4 reacted with hydrogen to reform LaMg 2 NiH 7 at 473 K under 1 MPa of H 2 gas pressure for 10 h. These results revealed that LaMg 2 NiH 7 exhibited partially reversible hydrogen-release and uptake reactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

All-solid-state batteries incorporating lithium metal anode have the potential to address the energy density issues of conventional lithium-ion batteries that use flammable organic liquid electrolytes and low-capacity carbonaceous anodes. However, they suffer from high lithium ion transfer resistance, mainly due to the instability of the solid electrolytes against lithium metal, limiting their use in practical cells. Here, we report a complex hydride lithium superionic conductor, 0.7Li(CB 9 H 10 )-0.3Li(CB 11 H 12 ), with excellent stability against lithium metal and a high conductivity of 6.7 × 10 -3  S cm -1 at 25 °C. This complex hydride exhibits stable lithium plating/stripping reaction with negligible interfacial resistance (<1 Ω cm 2 ) at 0.2 mA cm -2 , enabling all-solid-state lithium-sulfur batteries with high energy density (>2500 Wh kg -1 ) at a high current density of 5016 mA g -1 . The present study opens up an unexplored research area in the field of solid electrolyte materials, contributing to the development of high-energy-density batteries.

A complex hydride (LaMg 2 NiH 7 ) composed of La 3+ , two Mg 2+ , [NiH 4 ] 4- with a covalently bonded hydrogen, and three H - was formed from an intermetallic LaMg 2 Ni via an intermediate phase (LaMg 2 NiH 4.6 ) composed of La, Mg, NiH 2 , NiH 3 units, and H atoms at tetrahedral sites. The NiH 2 and NiH 3 units in LaMg 2 NiH 4.6 were reported as precursors for [NiH 4 ] 4- in LaMg 2 NiH 7 [ Miwa et al. J. Phys. Chem. C 2016 , 120 , 5926 - 5931 ]. To further understand the hydrogen states in the precursors (the NiH 2 and NiH 3 units) and H atoms at the tetrahedral sites in the intermediate phase, LaMg 2 NiH 4.6 , we observed the hydrogen vibrations in LaMg 2 NiH 4.6 and LaMg 2 NiH 7 by using inelastic neutron scattering. A comparison of the hydrogen vibrations of the NiH 2 and NiH 3 units with that of [NiH 4 ] 4- shows that the librational modes of the NiH 2 and NiH 3 units were nonexistent; librational modes are characteristic modes for complex anions, such as [NiH 4 ] 4- . Furthermore, the hydrogen vibrations for the H atoms in the tetrahedral sites showed a narrower wavenumber range than that for H - and a wider range than that for typical interstitial hydrogen. The results indicated the presence of intermediate hydrogen states before the formation of [NiH 4 ] 4- and H - .

Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH 9 ] 3- ), tungsten ([WH 9 ] 3- ), niobium ([NbH 9 ] 4- ) and tantalum ([TaH 9 ] 4- ) in novel complex transition-metal hydrides, Li 5 MoH 11 , Li 5 WH 11 , Li 6 NbH 11 and Li 6 TaH 11 , respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature.

Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2 B 12 H 12 , which contains large, icosahedral, divalent B 12 H 12 2- anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2 B 12 H 12 , possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11 H 12 and NaCB 11 H 12 salts, which contain icosahedral, monovalent CB 11 H 12 - anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (> 0.1 S cm -1 ) unmatched by any other known polycrystalline materials at these temperatures. With proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.

In a previous study, we used transmission electron microscopy and electron energy-loss (EEL) spectroscopy to investigate dehydrogenation of AlH₃ particles. In the present study, we systematically examine differences in the chemical bonding states of Al-containing compounds (including AlH₃) by comparing their Al-L 2,3 EEL spectra. The spectral chemical shift and the fine peak structure of the spectra were consistent with the degree of covalent bonding of Al. This finding will be useful for future nanoscale analysis of AlH₃ dehydrogenation toward the cell.

We describe a new method for the solvent-free synthesis of borohydrides at room temperature and demonstrate its feasibility by the synthesis of three of the most discussed borohydrides at present: LiBH(4), Mg(BH(4))(2) and Ca(BH(4))(2). This new gas-solid mechanochemical synthesis method is based on the reaction of metal hydrides with diborane to form the corresponding borohydrides. The synthesis will facilitate the preparation of a wide range of different borohydrides, including mixed borohydride systems, with tuneable sorption properties. We propose that diborane is an intermediate compound for the hydrogen sorption in borohydrides and may be the key for a reversible hydrogen ab- and desorption reaction under moderate conditions.