The present study highlights the first-ever application of fastest lithium (Li) ion conducting complex hydride containing cluster anions, namely lithium borohydride (LiBH4) into an all solid-state Li-ion battery having Bi2Te3 as anode material. Bi2Te3 nanostructures were prepared by the simple wet chemical method and characterized by their crystal structure, morphology and electronic structure using X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). SEM and TEM experiments revealed the dimensions as 20-60 nm for nanoparticles and 30-90 nm for nanosheets. The formation of Bi2Te3 nanostructures along with Bi2O3 as the residual phase is confirmed by XRD analysis. The crystallite size of nanoparticles and nanosheets are calculated as 19 nm and 39 nm respectively from XRD profile. The XPS study also confirms the formation of nanostructured Bi2Te3 along with Bi2O3. Finally, the electrochemical performance of these nanostructures is observed using the galvanostatic charge-discharge curve at 0.1C and 0.5C. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.