The escalating global energy crisis and the imperative to achieve carbon neutrality have intensified the demand for advanced energy storage technologies, particularly lithium-ion batteries which dominate applications in electric vehicles and grid-scale energy storage due to their high energy density and long cycle life. However, conventional graphite anodes face intrinsic limitations, including a low theoretical capacity (372 mAh/g) and safety risks associated with lithium dendrite formation during rapid charging. Titanium dioxide, particularly its anatase phase, has emerged as a promising alternative anode material owing to its structural stability, environmental benignity, and moderate lithium storage capacity (200 mAh/g). Despite these advantages, practical implementation of titanium dioxide anodes is hindered by sluggish lithium-ion diffusion kinetics and insufficient porosity in conventional synthesis methods. Micro-arc oxidation, a plasma-assisted electrochemical technique, enables in situ growth of oxide coatings on metallic substrates but typically yields dense, low-porosity films when using single-electrode configurations, limiting ion transport efficiency. To address these challenges, the work aims to pioneer a bi-electrodes micro-arc oxidation strategy, which is a novel dual-electrode discharge process that simultaneously generates porous anatase titanium dioxide coatings on both electrodes, enhancing structural and electrochemical performance without high-temperature post-processing. The bi-electrodes micro-arc oxidation process was implemented with a WH-20 system at a pulsed power supply (500 Hz frequency, 45% duty cycle) in an electrolyte containing Na3PO4 (8 g/L) and KOH. Titanium foils were treated at 17 A/dm for 2 minutes, enabling synchronized oxide layer growth on paired electrodes. Comparative analyses against conventional single-electrode micro-arc oxidation coatings revealed transformative structural improvements. X-ray diffraction and Raman spectroscopy confirmed the predominant anatase phase in BMAO-TiO2, evidenced by characteristic peaks at 25.3°, 38.4°, and 48.1° and distinct Raman modes at 146, 398, 513, and 638 cm-1. Scanning electron microscopy showed a hierarchical porous architecture with interconnected channels, achieving a porosity of 11.4% for BMAO-TiO2, a 27% increase over MAO-TiO2 (7.9%) attributed to the dual-electrode discharge mechanism that promoted uniform pore nucleation and growth. Electrochemical evaluations, including cyclic voltammetry, galvanostatic cycling, and rate capability tests, underscored the superiority of BMAO-TiO2: at 100 mA/g, it delivered a discharge capacity of 192.78 mAh/g after 200 cycles with >95% retention, outperforming MAO-TiO2 (176.48 mAh/g) by 9.2%. The lithium-ion diffusion coefficient surged to 1.26×10-14 cm2/s, a 34% enhancement over MAO-TiO2 (9.41×10-15 cm2/s), reflecting reduced ionic transport barriers. Rate performance tests exhibited 99% capacity recovery upon reverting to 50 mA/g after high-rate cycling (up to 1 000 mA/g), highlighting exceptional structural resilience. Electrochemical impedance spectroscopy further validated accelerated kinetics, with BMAO-TiO2 showing a 40% reduction in charge transfer resistance (smaller high-frequency semicircle diameter) and steeper Warburg slopes, indicative of faster Li+ diffusion. The initial Coulombic efficiency reached 64.5%, stabilizing near 100% in subsequent cycles, confirming highly reversible Li+ insertion/extraction. These advancements stem from the synergistic effects of bi-electrodes micro-arc oxidation. Firstly, the dual-electrode configuration generates uniform electric fields, fostering interconnected pores that facilitate electrolyte penetration and ion transport. Secondly, the enhanced crystallinity minimizes lattice defects, as evidenced by sharper XRD/Raman peaks, reducing charge recombination losses. Thirdly, the absence of post-synthetic annealing preserves the metastable anatase phase while eliminating energy-intensive processing steps. The bi-electrodes micro-arc oxidation technique not only addresses the porosity and kinetics limitations of traditional micro-arc oxidation but also offers a scalable, cost-effective route for industrial adoption. By circumventing high-temperature treatments, the process reduces manufacturing costs by an estimated 15%-20% compared to conventional sol-gel or hydrothermal methods. This study establishes bi-electrodes micro-arc oxidation as a paradigm-shifting approach for fabricating high-performance titanium dioxide anodes. The BMAO-derived coatings exhibit unparalleled porosity, lithium-ion diffusivity, and electrochemical stability, directly addressing the bottlenecks of LIB anode materials. With a discharge capacity of 192.78 mAh/g, capacity retention >95% over 200 cycles, and 99% rate recovery, BMAO-TiO2 surpasses state-of-the-art titanium dioxide based anodes, positioning it as a viable candidate for next-generation high-energy-density batteries. The simplicity, scalability and energy efficiency of the technique align with global sustainability agendas, offering a practical pathway to decarbonize energy storage systems. Future work will optimize electrolyte formulations and explore hybrid architectures (e.g. TiO2/graphene composites) to further elevate performance, paving the way for commercialization in electric mobility and renewable energy integration.
Key words
bi-electrodes micro-arc oxidation /
anode materials /
titanium dioxide /
lithium-ion batteries /
electrochemical performance
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Funding
National Natural Science Foundationof China (51672120); Natural Science Foundation of Heilongjiang Province (LH2023E101); the Scientific Research Projects of Provincial Colleges and Mudanjiang Normal University Teaching Reform Project (SJGYB2024687)
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