Molecular Precursor-Driven Synthesis of Copper Telluride Nanostructures for LIB Anode Application.

Copper tellurides have garnered substantial interest for their applicability as an electrocatalyst for water splitting, battery anodes and photodetectors, etc. Moreover, synthesis of phase pure metal tellurides using the multi-source precursor method is challenging. Therefore, a facile synthesis protocol for copper tellurides is anticipated. The current study involves a simplistic single source molecular precursor pathway for the synthesis of orthorhombic-Cu2.86Te2 nano blocks and -Cu31Te24 faceted nanocrystals employing the [Cu{TeC5H3(Me-5)N}]4 cluster in thermolysis and pyrolysis, respectively. The pristine nanostructures were carefully characterized by powder X-ray diffraction, energy-dispersive X-ray spectroscopy, electron microscopic techniques (scanning electron microscopy and transmission electron microscopy), and diffuse reflectance spectroscopy to know the crystal structure, phase purity, elemental composition, distribution of elements, morphology, and optical band gap. These measurements suggests that the reaction conditions fetch nanostructures of different sizes, crystal structures, morphologies, and band gaps. As prepared nanostructures were evaluated for lithium-ion batteries (LIBs) anode material. The cells fabricated with orthorhombic Cu2.86Te2 and orthorhombic Cu31Te24 nanostructures deliver capacities of 68 and 118 mA h/g after 100 cycles. The LIB anode made up of Cu31Te24 faceted nanocrystals exhibited good cyclability and mechanical stability.

Molecular precursor-mediated facile synthesis of phase pure metal-rich digenite (Cu1.8S) nanocrystals: an efficient anode for lithium-ion batteries.

Copper sulfides have gained significant attention as alternative electrodes for rechargeable batteries. A simple and easily scalable synthetic pathway to access these materials is highly desirable. This paper describes the facile synthesis of metal-rich digenite Cu1.8S nanocrystals from a structurally characterized new single-source molecular precursor in various high boiling solvents of varied polarity. The as-prepared nanostructures were thoroughly characterized by PXRD, Raman spectroscopy, EDS, XPS, electron microscopy techniques and diffuse reflectance spectroscopy to understand the crystal structure, phase purity, elemental composition, morphology and band gap. It was found that the reaction solvent has a profound role on their crystallite size, morphology and band gap, however the crystal structure and phase purity remained unaffected. Pristine Cu1.8S nanostructures have been employed as an anode material in lithium-ion batteries (LIBs). The cell delivers a high initial charge capacity of ∼462 mA h g-1 and retains a capacity of 240 mA h g-1 even after 300 cycles at 0.1 A g-1. DFT calculations revealed that multi-size polyhedron layers in the direction perpendicular to the two Li movement channels aid in the sustainable uptake of Li atoms with controlled volume expansion. The structure-mediated flexibility of the metal-rich Cu1.8S lattice during lithiation permits high cyclability with reasonable retention of capacity.

Dimethyltin(IV)-4,6-dimethyl-2-pyridylselenolate: an efficient single source precursor for the preparation of SnSe nanosheets as anode material for lithium ion batteries.

The air stable tin(IV) complex [Me2Sn{2-SeC5H2(Me-4,6)2N}2] has been synthesized, characterized by NMR, elemental analysis, and single crystal XRD, and employed as a single source molecular precursor (SSP) for the facile synthesis of orthorhombic SnSe nanosheets. The crystal structure, phase purity, morphology and band gap of the nanosheets were investigated by pXRD, EDS, electron microscopy and diffuse reflectance spectroscopy techniques, respectively. It was found that the preferential orientation of planes and the morphology of the nanosheets rely upon the reaction conditions. The band gaps of the nanosheets were blue shifted with respect to the bulk band gap of the material. The synthesized SnSe nanosheets have been employed as an anode material in lithium ion batteries (LIBs). The material exhibits an initial specific capacity of 1134 mA h g-1 at a current density of 50 mA g-1 and was found to retain a capacity of 380 mA h g-1 even after 70 cycles with 100% efficiency.

Optimization of lithium content in LiFePO4 for superior electrochemical performance: the role of impurities.

Carbon coated Li x FePO4 samples with systematically varying Li-content (x = 1, 1.02, 1.05, 1.10) have been synthesized via a sol-gel route. The Li : Fe ratios for the as-synthesized samples is found to vary from ∼0.96 : 1 to 1.16 : 1 as determined by the proton induced gamma emission (PIGE) technique (for Li) and ICP-OES (for Fe). According to Mössbauer spectroscopy, sample Li1.05FePO4 has the highest content (i.e., ∼91.5%) of the actual electroactive phase (viz., crystalline LiFePO4), followed by samples Li1.02FePO4, Li1.1FePO4 and LiFePO4; with the remaining content being primarily Fe-containing impurities, including a conducting FeP phase in samples Li1.02FePO4 and Li1.05FePO4. Electrodes based on sample Li1.05FePO4 show the best electrochemical performance in all aspects, retaining ∼150 mA h g-1 after 100 charge/discharge cycles at C/2, followed by sample Li1.02FePO4 (∼140 mA h g-1), LiFePO4 (∼120 mA h g-1) and Li1.10FePO4 (∼115 mA h g-1). Furthermore, the electrodes based on sample Li1.05FePO4 retain ∼107 mA h g-1 even at a high current density of 5C. Impedance spectra indicate that electrodes based on sample Li1.05FePO4 possess the least charge transfer resistance, plausibly having influence from the compositional aspects. This low charge transfer resistance is partially responsible for the superior electrochemical behavior of that specific composition.