Abstract
Lead lithium titanate (PbLi2Ti6O14) was synthesized by combustion route restricting the annealing at 900°C to just 1 minute. Rietveld analysis confirmed orthorhombic (Cmca) product phase with an average particle size ∼200 nm and surface area of 2 m2/g forming secondary porous particles. From bond valence site energy (BVSE) calculations, 1 D ionic conduction was found along c axis with low activation energy (0.23 eV). AC conductivity analysis revealed a bulk conductivity of 2 × 10−7 S.cm−1 at room temperature and 1 × 10−4 S.cm−1 at 200°C with a switch from extrinsic 1D to intrinsic 2D mechanism at 150°C. Li+ diffusion coefficient was calculated to be in the order of 10−12 cm2.s−1. More than 4 lithium (per f.u.) could be reversibly (de)inserted delivering capacity over 160 mAh/g with good cycling retention over 1000 cycles. With a feasible rapid synthesis, good diffusional and electrochemical behavior especially high rate capability, PbLi2Ti6O14 can act as a safe 1.35 V anode for rechargeable Li-ion batteries.
Highlights
A 4-fold surge in oil prices in 1973 marked the first energy crisis releasing a wave of urgency for alternate energy generation and its storage in chemical form.[1,2] Carbon as amorphous coal may be a polluting energy source, but in form of layered graphite, it is the cheapest and most widely used material for alternate energy storage in rechargeable lithium-ion batteries (LIBs)
Graphite suffers from issues like large irreversible capacity loss in the first cycle due to solid electrolyte interphase (SEI) formation,[6,7] lithium plating from dendrites during overcharge[89] and very low operating voltage
All these protocols involve expensive precursors and use of stable TiO2 that needs prolonged calcination (10–16 h), which calls for alternate energy conserving synthesis methods
Summary
A 4-fold surge in oil prices in 1973 marked the first energy crisis releasing a wave of urgency for alternate energy generation and its storage in chemical form.[1,2] Carbon as amorphous coal may be a polluting energy source, but in form of layered graphite, it is the cheapest and most widely used material for alternate energy storage (or power source) in rechargeable lithium-ion batteries (LIBs). Graphite suffers from issues like large irreversible capacity loss in the first cycle due to solid electrolyte interphase (SEI) formation (below 0.8V),[6,7] lithium plating from dendrites during overcharge[8] (or at high currents)[9] and very low operating voltage These factors limit the safe usage of batteries having graphite anodes for mobile applications requiring fast charging such as power tool, start-stop application and regenerative braking. To this end, a large number of safe Ti-based materials[10,11,12] have been investigated leading to successful commercialization of spinel Li4Ti5O12 (LTO) anode[13] with high operating voltage and low volume change. Onedimensional diffusion pathways with moderate energy barrier and intermediate voltage safe operation at high C rates, combustion made PbLi2Ti6O14 presents a viable candidate for rechargeable LIB anode
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