Biopolymer‐assisted Synthesis of P‐doped TiO₂ Nanoparticles for High‐performance Lithium‐ion Batteries: A Comprehensive Study

Abstract

TiO2 material has gained significant attention for large‐scale energy storage due to its abundant, low‐cost, and environmentally friendly properties, as well as the availability of various nanostructures. Phosphorus doping has been established as an effective technique for improving electronic conductivity and managing the slow ionic diffusion kinetics of TiO2. In this study, non‐doped and phosphorus doped TiO2 materials were synthesized using sodium alginate biopolymer as chelating agent. The prepared materials were evaluated as anode materials for Lithium‐Ion Batteries (LIBs). The electrodes exhibit remarkable electrochemical performance, including a high reversible capacity of 235 mAh g‐1 at 0.1C and excellent first coulombic efficiency of 99%. An integrated approach, combining Operando XRD and Ex‐situ XAS, comprehensively investigates the relationship between phosphorus doping, material structure, and electrochemical performance, reinforced by analytical tools and first principles calculations. Furthermore, a full cell was designed using 2%P‐doped TiO2 anode and LiFePO4 cathode. The output voltage was about 1.6V with high initial specific capacity of 148 mAh g‐1, high rate‐capability of 120 mAh g‐1 at 1C, and high‐capacity retention of 96% after 1000 cycles at 1C.

The Electrochemical and Structural Changes of Phosphorus-Doped TiO2 through In Situ Raman and In Situ X-Ray Diffraction Analysis

“…Anatase titanium oxide TiO 2 and P-doped TiO 2 nanoparticles were synthesized using the sol–gel method, following the procedure outlined by Karim et al , A volume V1 of titanium­(IV) isopropoxide solution (99.999% trace metals base, Sigma-Aldrich) was mixed with 100 mL of ethanol absolute (Sigma-Aldrich), and then a volume V2 of phosphoric acid solution was added to the mixture (Sigma-Aldrich) under magnetic stirring. Table presents the volumes for each doping level.…”

“…The delithiation capacity of Zr 4+ /F – codoped TiO 2 is still as high as 138 mAh g –1 even at a cycling rate of 10C . Phosphorus-doped TiO 2 synthesized using recycled human urine displayed an initial discharge capacity of 214 mAh g –1 , maintaining 159 mAh g –1 even after 100 cycles. , …”

“… 18 Phosphorus-doped TiO 2 synthesized using recycled human urine displayed an initial discharge capacity of 214 mAh g –1 , maintaining 159 mAh g –1 even after 100 cycles. 21 , 22 …”

Limiting voltage and capacity fade of lithium-rich, low cobalt Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 by controlling the upper cut-off voltage

“…The coin cells were assembled in an Ar-lled glovebox using lithium foil as counter electrodes, WHATMAN glass microber lter as separator and 1 M LiPF 6 in EC : DMC (1 : 1) as electrolyte. For Full Cell measurement, P-doped TiO 2 (synthesis process and electrochemical performances are details in our recent studies 71,72 ) was used as negative electrode. This electrode was composed of 85% wt of P-doped TiO 2 active material, 10% wt of carbon black, and 5% wt PVDF.…”

Beyond conventional batteries: a review on semi-solid and redox targeting flow batteries-LiFePO4 as a case study

“…To promote the utilization of renewable and sustainable energy and also enhance the stability of grid networks, energy storage systems are needed to store excess electricity. 1–6 For this reason, flow batteries have been developed. This flexible and modular process can be scaled very precisely according to the power and energy requirements of a renewable energy plant.…”