LiCe(BH4)3Cl, a New Lithium-Ion Conductor and Hydrogen Storage Material with Isolated Tetranuclear Anionic Clusters

Mechanochemical synthesis using CeCl 3-MBH 4 (M = Li, Na or K) mixtures are investigated and produced a new compound, LiCe(BH 4) 3Cl, which crystallizes in a cubic space group I43m, a = 11.7204(2) A. The structure contains isolated tetranuclear anionic clusters [Ce 4Cl 4(BH 4) 12] 4- with a distorted cubane Ce 4Cl 4 core, charge-balanced by Li + cations. Each Ce atom coordinates three chloride ions and three borohydride groups via the I• 3- BH 3 faces, thus completing the coordination environment to an octahedron. Combination of synchrotron radiation powder X-ray diffraction (SR-PXD), powder neutron diffraction and density functional theory (DFT) optimization show that Li cations are disordered, occupying 2/3 of the 12d Wyckoff site. DFT calculation indicates that LiCe(BH 4) 3Cl is stabilized by higher entropy rather than lower enthalpy, in accord with the disorder in Li positions. The structural model also agrees well with the very high lithium ion conductivity measured for LiCe(BH 4) 3Cl of 1 A - 10 -4 Scm -1 at T = 20 °C. In situ SR-PXD reveals that the decomposition products consist of LiCl, CeB 6 and CeH 2. The Sieverts measurements show that 4.7 wt % H 2 is released during heating to 500 °C. After rehydrogenation at 400 °C and p(H 2) = 100 bar for 24 h an amount of 1.8 wt % H 2 is released in the second dehydrogenation. The 11B MAS NMR spectra of the central and satellite transitions for LiCe(B(D/H) 4) 3Cl reveal highly asymmetric manifolds of spinning sidebands from a single 11B site, reflecting dipolar couplings of the 11B nuclear spin with the paramagnetic electron spin of the Ce 3+ ions. © 2012 American Chemical Society.