We report an investigation of the pseudo-photocatalytic behavior of rutile TiO2 nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a “light” source to initiate the catalytic reaction and a “water-in-salt” aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO2 nanorod under a low electron dose rate (9.3–18.6 e-/Å2·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Å2 ·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO2 nanorods is further validated using density functional theory (DFT)calculation. Our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces.

The practical application of high-capacity Li-rich cathode materials is hindered by capacity fading and voltage decay. The capacity fading and voltage decay could be effectively overcome by using water-soluble guar gum (GG) binder instead of traditional polyvinylidene fluoride (PVDF). However, the specific role of the GG binder is not clear yet, though the GG binder can significantly improve the electrochemical performance of Li-rich cathode. To understand the effect of GG binder on the morphology, microstructure of electrode and electrode/electrolyte interfaces, ex-situ scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray adsorption near edge spectroscopy (XANES), in-situ electrochemical impedance spectroscopy (EIS) were applied to comparatively study the charge-discharge processes of Li-rich Li1.2Ni0.2Mn0.6O2 cathode when using GG and PVDF as binders. The results indicate that the GG binder can prevent electrode crack and active material loss, ascribing to the strong mechanical adhesion of GG binder with active material particles and current collector. It has found that the GG binder can also induce the formation of a uniform layer on Li1.2Ni0.2Mn0.6O2 particles’ surface. As a consequence, both the electrolyte decomposition and the electrode corrosion were significantly inhibited. The strong chelation between Mn2+ and polar OH group restrain Mn ion dissolution, which contributes to surface structural transformation mitigation. The present study reveals the role of water-soluble GG binder in reducing capacity fading and voltage decay of Li-rich material and is of great importance in design functional binders for high-performance Li-rich electrodes.

The first-cycle behavior of layered Li-rich oxides, including Li₂MnO₃ activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li₂MnO₃ activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi₂MnO₃·(1- x) LiNi_0.3Co_0.3Mn_0.4O₂ ( x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li₂MnO₃ and LiNi_0.3Co_0.3Mn_0.4O₂ structures can significantly affect the activation pathway of Li_1.2Ni_0.12Co_0.12Mn_0.56O₂, leading to an extra-high capacity. It is demonstrated that Li₂MnO₃ activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li₂MnO₃ governed by chemical decomposition (Li₂O evolution). CEI evolution is closely related to Li⁺ extraction/insertion. The valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.