Anomalous Impact of Mechanochemical Treatment on the Na-ion Conductivity of Sodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy.

Solid-state sodium ion conductors are crucial for the next generation of all-solid-state sodium batteries with high capacity, low cost, and improved safety. Sodium closo-carbadodecaborate (NaCB11 H12 ) is an attractive Na-ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all-solid-state sodium batteries. Intriguingly, milling longer than 2 h led to a significant decrease in conductivity. In this study, X-ray Raman scattering (XRS) spectroscopy is used to probe the origin of the anomalous impact of mechanical treatment on the ionic conductivity of NaCB11 H12 . The B, C, and Na K-edge XRS spectra are successfully measured for the first time, and ab initio calculations are employed to interpret the results. The experimental and computational results reveal that the decrease in ionic conductivity upon prolonged milling is due to the increased proximity of Na to the CB11 H12 cage, caused by severe distortion of the long-range structure. Overall, this work demonstrates how the XRS technique, allowing investigation of low Z elements such as C and B in the bulk, can be used to acquire valuable information on the electronic structure of solid electrolytes and battery materials in general.

Thermal Polymorphism in CsCB11H12.

Thermal polymorphism in the alkali-metal salts incorporating the icosohedral monocarba-hydridoborate anion, CB11H12-, results in intriguing dynamical properties leading to superionic conductivity for the lightest alkali-metal analogues, LiCB11H12 and NaCB11H12. As such, these two have been the focus of most recent CB11H12- related studies, with less attention paid to the heavier alkali-metal salts, such as CsCB11H12. Nonetheless, it is of fundamental importance to compare the nature of the structural arrangements and interactions across the entire alkali-metal series. Thermal polymorphism in CsCB11H12 was investigated using a combination of techniques: X-ray powder diffraction; differential scanning calorimetry; Raman, infrared, and neutron spectroscopies; and ab initio calculations. The unexpected temperature-dependent structural behavior of anhydrous CsCB11H12 can be potentially justified assuming the existence of two polymorphs with similar free energies at room temperature: (i) a previously reported, ordered R3 polymorph stabilized upon drying and transforming first to R3c symmetry near 313 K and then to a similarly packed but disordered I43d polymorph near 353 K and (ii) a disordered Fm3 polymorph that initially appears from the disordered I43d polymorph near 513 K along with another disordered high-temperature P63mc polymorph. Quasielastic neutron scattering results indicate that the CB11H12- anions in the disordered phase at 560 K are undergoing isotropic rotational diffusion, with a jump correlation frequency [1.19(9) × 1011 s-1] in line with those for the lighter-metal analogues.

Structural Phase Transitions in closo-Dicarbadodecaboranes C2B10H12.

The crystal structures of three thermal polymorphs (I, II, and III) for each isomer of closo-dicarbadodecaboranes C2B10H12 (ortho, meta, and para) have been determined by combining synchrotron radiation X-ray powder diffraction and density functional theory calculations. The structures are in agreement with previous calorimetric and spectroscopic studies. The difference between rotatory phases (plastic crystals) I and II lies in isotropic rotations in the former and anisotropic rotations of the icosahedral clusters in the latter. Phase I is the cubic close packing (ccp) of rotating closo-molecules C2B10H12 in the space group Fm3̅. Phase II is the ccp of rotating closo-molecules C2B10H12 in the cubic space group Pa3̅. The preferred rotational axis in II varies with the isomer. The ordered phases III are orthorhombic (meta) or monoclinic (ortho and para) deformations of the cubic unit cell of the disordered phases I and II. The ordering in the phase III of the ortho-isomer carrying the biggest electrical dipole moment creates a twofold superstructure w.r.t. the cubic unit cell. The thermal polymorphism for C2B10H12 and related metal salts can be explained by division of the cohesive intercluster interactions into two categories (i) dispersive cohesive interaction with additional Coulombic components in the metal salts and (ii) anisotropic local interaction resulting from nonuniform charge distribution around icosahedral clusters. The local interactions are averaged out by thermally activated cluster dynamics (rotations and rotational jumps) which effectively increase the symmetry of the cluster. The C2B10H12 molecules resist at least as well as the CB11H12- anion to the oxidation, and both clusters form easily a mixed compound. This allows designing solid electrolytes such as Nax(CB11H12)x(C2B10H12)1-x, where the cation content may be varied and the temperature of transition into the disordered conducting phase is decreased.

Enhanced Room-Temperature Ionic Conductivity of NaCB11H12 via High-Energy Mechanical Milling.

The body-centered cubic (bcc) polymorph of NaCB11H12 has been stabilized at room temperature by high-energy mechanical milling. Temperature-dependent electrochemical impedance spectroscopy shows an optimum at 45-min milling time, leading to an rt conductivity of 4 mS cm-1. Mechanical milling suppresses an order-disorder phase transition in the investigated temperature range. Nevertheless, two main regimes can be identified, with two clearly distinct activation energies. Powder X-ray diffraction and 23Na solid-state NMR reveal two different Na+ environments, which are partially occupied, in the bcc polymorph. The increased number of available sodium sites w.r.t. ccp polymorph raises the configurational entropy of the bcc phase, contributing to a higher ionic conductivity. Mechanical treatment does not alter the oxidative stability of NaCB11H12. Electrochemical test on a symmetric cell (Na|NaCB11H12|Na) without control of the stack pressure provides a critical current density of 0.12 mA cm-2, able to fully charge/discharge a 120 mA h g-1 specific capacity positive electrode at the rate of C/2.

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH4-MgO Composite Electrolyte.

LiBH4 has been widely studied as a solid-state electrolyte in Li-ion batteries working at 120 °C due to the low ionic conductivity at room temperature. In this work, by mixing with MgO, the Li-ion conductivity of LiBH4 has been improved. The optimum composition of the mixture is 53 v/v % of MgO, showing a Li-ion conductivity of 2.86 × 10-4 S cm-1 at 20 °C. The formation of the composite does not affect the electrochemical stability window, which is similar to that of pure LiBH4 (about 2.2 V vs Li+/Li). The mixture has been incorporated as the electrolyte in a TiS2/Li all-solid-state Li-ion battery. A test at room temperature showed that only five cycles already resulted in cell failure. On the other hand, it was possible to form a stable solid electrolyte interphase by applying several charge/discharge cycles at 60 °C. Afterward, the battery worked at room temperature for up to 30 cycles with a capacity retention of about 80%.

Insights into the Rb-Mg-N-H System: an Ordered Mixed Amide/Imide Phase and a Disordered Amide/Hydride Solid Solution.

The crystal structure of a mixed amide-imide phase, RbMgND2ND, has been solved in the orthorhombic space group Pnma ( a = 9.55256(31), b = 3.70772(11) and c = 10.08308(32) Å). A new metal amide-hydride solid solution, Rb(NH2) xH(1- x), has been isolated and characterized in the entire compositional range. The profound analogies, as well as the subtle differences, with the crystal chemistry of KMgND2ND and K(NH2) xH1- x are thoroughly discussed. This approach suggests that the comparable performances obtained using K- and Rb-based additives for the Mg(NH2)2- 2LiH and 2LiN H2-MgH2 hydrogen storage systems are likely to depend on the structural similarities of possible reaction products and intermediates.

Modified Anion Packing of Na2B12H12 in Close to Room Temperature Superionic Conductors.

Three different types of anion packing, i.e., hexagonal close packed (hcp), cubic close packed (ccp), and body centered cubic (bcc), are investigated experimentally and with ab initio calculations in the model system Na2B12H12. Solvent free and water assisted mechanical grinding provide polycrystalline samples for temperature-dependent synchrotron radiation X-ray powder diffraction and electrochemical impedance spectroscopy. It is shown that among the common close packed lattices, the hcp anionic backbone creates very favorable conditions for three-dimensional ionic conduction pathways, comprised of O-O, T-T, and T-O-T (O for octahedral, T for tetrahedral) cation hops. The hcp lattice is stable with respect to ccp and bcc lattices only at higher volumes per formula unit, which is achieved either by cationic substitution with larger cations or partial substitution of hydrogen by iodine on the closo-anion. It is found that the partial cationic substitution of sodium with lithium, potassium, or cesium does not lead to enhanced conductivity due to the obstruction of the conduction pathway by the larger cation located on the octahedral site. Substitution on the closo-anion itself shows remarkable positive effects, the ionic conductivity of Na2B12H12-xIx reaching values of close to 10-1 S cm-1 at a rather low temperature of 360 K. While the absolute value of σ is comparable to that of NaCB11H12, the temperature at which it is attained is approximately 20 K lower. The activation energy of 140 meV is determined from the Arrhenius relation and among the lowest ever reported for a Na-conducting solid.