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Abstract Traditional linear carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) were investigated as co-solvents for the dimethyl-2,5-dioxahexane carboxylate (DMOHC)-based electrolyte in Na0.97Ca0.03[Mn0.39Fe0.31Ni0.22Zn0.08]O2 (NCMFNZO)/hard carbon (HC) pouch cells. The EMC-containing cell displays excellent electrochemical performance, exhibiting only a 1.6 mAh irreversible capacity loss during 500 hours of storage at 4V and 40°C, and maintaining over 80% capacity retention after 200 cycles up to 4V at 40°C. Severe gas evolution and Na plating issues are present in all the tested systems. 

Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase (CEI) decay are intensely discussed in the field. Synchrotron X-ray and neutron scattering characterization techniques offer unique capabilities for investigating the complex structure and dynamics of high-voltage cathode behavior. In this review, to accelerate the development of stable high-voltage SIBs, we provide a comprehensive and thorough overview of the use of synchrotron X-ray and neutron scattering in studying SIB cathode materials with an emphasis on high-voltage layered transition metal oxide cathodes. We then discuss these characterizations in relation to polyanion-type cathodes, Prussian blue analogues, and organic cathode materials. Finally, future directions of these techniques in high-voltage SIB research are proposed, including CEI studies for polyanion-type cathodes and the extension of neutron scattering techniques, as well as the integration of morphology and phase characterizations. 

The effects of fluoroethylene carbonate (FEC) electrolyte additive on charged sodium ion electrode/electrolyte reactivity at elevated temperatures were investigated using accelerating rate calorimetry (ARC). The beneficial effect of FEC on cell lifetime was demonstrated using Na_0.97Ca_0.03[Mn_0.39Fe_0.31Ni_0.22Zn_0.08]O₂(NCMFNZO)/hard carbon (HC) pouch cells first prior to ARC measurements. Electrodes from these pouch cells were utilized as sample materials and 1.0 M NaPF₆in propylene carbonate (PC):ethyl methyl carbonate (EMC) (1:1 by vol.) was chosen as control electrolyte. Adding 2 wt% and 5 wt% FEC to the electrolyte does not significantly affect the reactivity of de-sodiated NCMFNZO compared to the control electrolyte. However, the addition of FEC obviously changed the reactivity between sodiated HC and electrolytes, especially by showing a suppression on the exothermal behavior between 160 °C and 230 °C. These results give a head to head comparison of the reactivity of FEC additive containing electrolytes with charged sodium ion electrode materials at elevated temperatures and show that the use of FEC at additive levels should not compromise the cell safety when extending cell lifetime. 

Despite extensive research efforts in developing aqueous rechargeable zinc metal batteries (RZMBs) as high-energy-density alternatives to both lithium ion and lithium metal batteries, the commercial prospects for RZMBs are still obfuscated by fundamental scientific questions. In particular, the electrode–electrolyte interphase properties and behaviors are still intensely debated topics in this field. In this review, we provide a comprehensive and thorough overview of the solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) in aqueous RZMBs, with an emphasis on the formation mechanisms and characteristics of the SEI and CEI. We then summarize state-of-the-art techniques for characterizing the SEI/CEI to reveal the intrinsic correlation between the functionalities of the interphases and the electrochemical performances. Finally, future directions are proposed, including studies on aqueous SEI/CEI evolution as a function of pH and temperature, as well as SEI/CEI studies for high-energy-density and long-lifetime RZMBs.