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Robust Surface [BO3] Gradient Integration: Nanoscale Engineering for Enhanced Environmental Stability of Sodium
Sheng Xu1,2, Rixin Liu1,2, Zhaoguo Liu1,2
1College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid-State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing210093, China.
This study introduces a nanoscale surface coating for sodium-ion battery cathodes, significantly improving their stability against moisture and air. This breakthrough enhances long-term performance and commercial viability for large-scale energy storage.
Area of Science:
- Materials Science
- Electrochemistry
- Nanotechnology
Background:
- Sodium-ion batteries are crucial for large-scale energy storage but face commercialization hurdles due to the environmental sensitivity of layered cathode materials.
- Existing methods struggle to prevent water intercalation and cation exchange while preserving electrochemical performance.
Purpose of the Study:
- To develop a nanoscale surface engineering strategy to enhance the environmental stability of layered oxide cathodes for sodium-ion batteries.
- To address simultaneous water intercalation and cation exchange issues affecting cathode performance.
Main Methods:
- Nanoscale surface engineering via formation of a ~20 nm [BO3] gradient on layered oxide cathode surfaces.
- Characterization using Electron Energy Loss Spectroscopy (EELS) and Density Functional Theory (DFT) calculations.
- Electrochemical testing of surface-modified P2-Na0.67Mn0.88Al0.12B0.05O2 (NMABO) and commercial O3-NaNi1/3Fe1/3Mn1/3O2 cathodes.
Main Results:
- The [BO3] gradient interface coordinated with [MnO6] polyhedra, confirmed by EELS and DFT.
- NMABO cathodes achieved 176 mAh g-1 initial capacity with 80.1% retention after 1000 cycles at 10C.
- Engineered cathodes showed excellent moisture resistance (80.3% capacity retention after 1300 cycles post-air exposure) and stability after 2-year storage.
- The [BO3] gradient inhibited Jahn-Teller distortion and prevented H2O intercalation and Na+/H+ exchange.
- The strategy was validated on commercial O3-NaNi1/3Fe1/3Mn1/3O2 cathodes, showing robust stability in humid air.
Conclusions:
- A scalable nanoscale interface design approach enhances the environmental stability of sodium layered oxides.
- The [BO3] gradient effectively addresses fundamental degradation issues in ambient conditions, paving the way for commercialization.
- This surface engineering strategy offers a universal solution for improving the durability of sodium-ion battery cathodes.
