Revisiting the Charging Mechanism of α-MnO2 in Mildly Acidic Aqueous Zinc Electrolytes.

In recent years, there have been extensive debates regarding the charging mechanism of MnO2 cathodes in aqueous Zn electrolytes. The discussion centered on several key aspects including the identity of the charge carriers contributing to the overall capacity, the nature of the electrochemical process, and the role of the zinc hydroxy films that are reversibly formed during the charging/discharging. Intense studies are also devoted to understanding the effect of the Mn2+ additive on the performance of the cathodes. Nevertheless, it seems that a consistent explanation of the α-MnO2 charging mechanism is still lacking. To address this, a step-by-step analysis of the MnO2 cathodes is conducted. Valuable information is obtained by using in situ electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, supplemented by solid-state nuclear magnetic resonance (NMR), X-ray diffraction (XRD) in Characterization of Materials, and pH measurements. The findings indicate that the charging mechanism is dominated by the insertion of H3O+ ions, while no evidence of Zn2+ intercalation is found. The role of the Mn2+ additive in promoting the generation of protons by forming MnOOH, enhancing the stability of Zn/α-MnO2 batteries is thoroughly investigated. This work provides a comprehensive overview on the electrochemical and the chemical reactions associated with the α-MnO2 electrodes, and will pave the way for further development of aqueous cathodes for Zn-ion batteries.

Solvation Engineering via Fluorosurfactant Additive Toward Boosted Lithium-Ion Thermoelectrochemical Cells.

Lithium-ion thermoelectrochemical cell (LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat-to-current behavior limit the application of LTECs using LiPF6 electrolyte. Introducing additives into bulk electrolyte is a reasonable strategy to solve such problem by modifying the solvation structure of electrolyte ions. In this work, we develop a dual-salt electrolyte with fluorosurfactant (FS) additive to achieve high thermopower and durability of LTECs during the conversion of low-grade heat into electricity. The addition of FS induces a unique Li+ solvation with the aggregated double anions through a crowded electrolyte environment, resulting in an enhanced mobility kinetics of Li+ as well as boosted thermoelectrochemical performances. By coupling optimized electrolyte with graphite electrode, a high thermopower of 13.8 mV K-1 and a normalized output power density of 3.99 mW m-2 K-2 as well as an outstanding output energy density of 607.96 J m-2 can be obtained. These results demonstrate that the optimization of electrolyte by regulating solvation structure will inject new vitality into the construction of thermoelectrochemical devices with attractive properties.