Sodium-ion batteries (NIBs) have been emerging as one of the most promising candidates for stationary storage applications such as telecommunication towers, micro-grids etc., mainly because Na is one of the most abundant elements on the Earth’s crust.^1,2 NIB operating at ambient temperature is expected to be durable, safe and inexpensive. Regardless of the relatively lower energy density of NIBs, they can be effectively employed for stationary applications, where the weight and footprint requirements are not severe.³ However, identifying appropriate anode, cathode, electrolyte, as well as the combination of these three components have always been challenging to develop robust NIB.^4,5

In this talk, we will present investigation of the storage performance, thermal stability⁶ and SEI layers of four notable anodes, viz., hard carbon, graphite, TiO₂ and Na₂Ti₃O₇⁷ using ether-based non-flammable electrolyte: 1M NaBF₄ in tetraglyme and compare with the results obtained with commonly used carbonate-based electrolyte: 1M NaClO₄ in EC:PC. We report better storage performance with higher first cycle coulombic efficiency of above anodes tested against metallic Na using ether-based electrolyte compared to carbonate-based electrolytes. Thermal studies, ATR-FTIR and impedance spectroscopy recorded at fully sodiated and fully desodiated states of these four anodes further confirm that a more stabilized SEI is formed by ether-based electrolyte. Above studies further suggests that the ether-based electrolyte is much safer for NIBs compared to carbonate-based electrolytes such as 1M NaClO₄ in EC:PC.

For the cathode, Na₃V₂(PO₄)₃ (NVP) was chosen due to a high redox potential of 3.37 V vs. Na/Na⁺. By employing a highly scalable synthesis procedure⁸ two types of NVP are prepared: pristine NVP and modified NVP by aliovalent doping. Sodium storage performances (specific capacity, rate performance and cycle life) of modified NVP outperforms the pristine NVP. The observed superior storage performance in modified NVP is attributed to enhanced activity of vanadium (V³⁺ to V⁴⁺ and V⁴⁺ to V⁵⁺)⁹ as confirmed by XPS studies and higher chemical diffusion coefficient.

We also present storage performance, XPS studies, measurement of heat loss and internal resistance of 18650-type non-flammable NIB cells made using NVP (pristine- and modified- NVP) vs. HC with 1M NaBF₄ in tetraglyme as electrolyte. The 18650 cell of pristine NVP vs. HC shows low energy density (47 Wh.kg⁻¹), moderate rate performance and poor cyclability. On the other hand, the 18650 cell of modified NVP vs. HC exhibits improved energy density (60 Wh.kg⁻¹) and enhanced rate and cyclic performances. Further, we report lesser heat generation in modified NVP vs. HC cell compared to pristine NVP vs. HC cell. Corresponding internal resistance of these 18650 cells measured at different depths of discharge (DoD) and temperature intervals reveal improved chemical diffusion coefficient, and substantial reduction in charge transfer resistance of the modified NVP vs. HC cell caused by aliovalent doping of NVP.

The work presented here for introducing a safe NIB technology for stationary storage application is an illustration of R&D with a long value chain: scale-up production of cathode materials, commercial type cell fabrication, investigation of storage performance, estimation of heat generation, quantification of heat loss in terms of internal resistance. This translational R&D at NUS thus bridges academics and industries.

References:

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