Overcoming Ion Transport Barrier by Plasma Heterointerface Engineering: Epitaxial Titanium Carbonitride on Nitrogen-Doped TiO2 for High-Performance Sodium-Ion Batteries

Qianli Cai; Xinglong Li; Ertao Hu; Zhongyue Wang; Peng Lv; Jiajin Zheng; Kehan Yu; Wei Wei; Kostya Ken Ostrikov

doi:10.1002/smll.202200694

Overcoming Ion Transport Barrier by Plasma Heterointerface Engineering: Epitaxial Titanium Carbonitride on Nitrogen-Doped TiO₂ for High-Performance Sodium-Ion Batteries

Small. 2022 Apr;18(16):e2200694. doi: 10.1002/smll.202200694. Epub 2022 Mar 10.

Authors

Qianli Cai¹, Xinglong Li¹, Ertao Hu¹, Zhongyue Wang¹, Peng Lv¹, Jiajin Zheng¹, Kehan Yu^{1

2}, Wei Wei^{1

2}, Kostya Ken Ostrikov^{3

4}

Affiliations

¹ School of Electronic and Optical Engineering, Nanjing University of Posts and Telecommunications, Nanjing, 210023, China.
² Jiangsu Province Engineering Research Center for Fabrication and Application of Special Optical Fiber Materials and Devices, Nanjing, 210036, China.
³ School of Chemistry and Physics and QUT Centre for Materials Science, Queensland University of Technology (QUT), Brisbane, QLD, 4000, Australia.
⁴ CSIRO-QUT Joint Sustainable Processes and Devices Laboratory P.O. Box 218, Lindfield, NSW, 2070, Australia.

PMID: 35266638
DOI: 10.1002/smll.202200694

Abstract

Anatase TiO₂ is a promising anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) due to its high specific capacity, low cost, and excellent cycle stability. However, low electrical conductivity and poor Na⁺ ion transport in TiO₂ limit its practical applications. Here, substantially boosted Na⁺ ion transport and charge transfer kinetics are demonstrated by constructing a near-ideal non-rectifying titanium carbonitride/nitrogen-doped TiO₂ (TiC_x N_1- _x /N-TiO₂ ) heterostructure. Owing to the fast plasma effects and metastable hybrid phases, the TiC_x N_1- _x is epitaxially grown on TiO₂ . Energy band engineering at the interface induces high electron densities and a strong built-in electric field, which lowers the Na⁺ diffusion barrier by a factor of 1.7. As a result, the TiC_x N_1- _x /N-TiO₂ electrode exhibits excellent electrochemical performance. The reversible specific capacities at rates of 0.1 and 10 C reach 312.3 and 173.7 mAh g^-1 , respectively. After 600 cycles of charge and discharge at 10 C, the capacity retention rate is 98.7%. This work discovers an effective non-equilibrium plasma-enabled process to construct heterointerfaces that can enhance Na⁺ ion transport and provides generic guidelines for the design of heterostructures for a broader range of energy storage, separation, and other devices that rely on controlled ionic transport.

Keywords: diffusion barriers; heterostructures; plasma; sodium-ion batteries; titanium carbonitride; titanium dioxide.

Abstract

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