This research aims to evaluate the influence of different 3D metals (Fe, Co, and Ni) substituted to Mn on the electrochemical performance of P2-NaxMe1/3Mn2/3O2 material, which was synthesized by the coprecipitation process followed by calcination at high temperature. X-ray diffraction (XRD) results revealed that the synthesized Mn-rich materials possessed a P2-type structure with a negligible amount of oxide impurities. The materials possessed their typical cyclic voltammogram and charge-discharge profiles; indeed, a high reversible redox reaction was obtained by NaxCo1/3Mn2/3O2 sample. Both NaxCo1/3Mn2/3O2 and NaxFe1/3Mn2/3O2 provided a high specific capacity of above 140 mAh·g−1; however, the former showed better cycling performance with 83% capacity retention after 50 cycles at C/10 and high rate capability. Meanwhile, the Ni-sub NaxNi1/3Mn2/3O2 exhibited excellent cycling stability but a low specific capacity of 110 mAh·g−1 and inferior rate capability. The diffusion coefficient of Na+ ions into the structure tended to decrease with a depth of discharge; those values were in the range of 10−10–10−9 cm2·s−1 and 10−11–10−10 cm2·s−1 in the solid solution region and biphasic region, respectively.

Introduction: Sulfolane (SL), having an edge of low melting point over other sulfones, has been adopted as an electrolyte co-solvent for lithium-ion battery (LIB), as it exhibits high stability against oxidation and combustion while not causing much side effects to the battery electrochemistry. It is therefore expected that SL may serve as a safety-enhancing agent in sodium-ion battery (SIB). To evaluate the effect of SL content on the behavior of common carbonate-based sodium electrolytes as well as the compatibility of SL-based electrolytes with NaNi1=3Mn1=3Co1=3O2 (NaNMC) cathode, mixtures of 0, 10, 20, 30 or 50% vol. SL and each of the following, EC:PC 1:1 vol. (EP11), EC:DMC 1:1 vol. (ED11), EC:PC:DMC 1:1:3 vol. (EPD113) and EC:PC:DMC 3:1:1 vol. (EPD311), with or without 1M NaClO4, were studied with regard to both inherent properties and performance in NaNMC half-cells. Methods: Solvent flammability was evaluated via the self-extinguishing time (SET) and ignition time indexes. Conductivity and viscosity were respectively measured by Electrochemical Impedance Spectroscopy (EIS) and Ostwald method. Electrochemical techniques, i.e. Cyclic Voltammetry (CV) and Galvanostatic Cycling with Potential Limitation (GCPL), were used to test the sodium-ion battery performance. Results: A moderate amount of SL (typically below 30% vol.) proved to enhance both electrolyte non-flammability and self-extinguishing behavior, while maintaining an acceptable compromising rate in viscosity and conductivity. Amongst 30%-SL electrolytes, EPD311-based ones allow the best Na+ diffusion when combined with NaNMC cathode in sodium half-cell configuration. The corresponding system gives satisfactory performance: initial specific capacity of 97 mAh.g-1, 92% capacity retention, and above 90% reversibility after 30 cycles at C/10 rate. Conclusion: SL can be used as a stabilizing co-solvent for SIB, but its content should be limited to below 30% vol. to ensure its effectiveness.