The increasing demands of energy storage require the significant improvement of current Li-ion battery electrode materials and the development of advanced electrode materials. Thus, it is necessary to gain an in-depth understanding of the reaction processes, degradation mechanism, and thermal decomposition mechanisms under realistic operation conditions. This understanding can be obtained by in situ/operando characterization techniques, which provide information on the structure evolution, redox mechanism, solid-electrolyte interphase (SEI) formation, side reactions, and Li-ion transport properties under operating conditions. Here, the recent developments in the in situ/operando techniques employed for the investigation of the structural stability, dynamic properties, chemical environment changes, and morphological evolution are described and summarized. The experimental approaches reviewed here include X-ray, electron, neutron, optical, and scanning probes. The experimental methods and operating principles, especially the in situ cell designs, are described in detail. Representative studies of the in situ/operando techniques are summarized, and finally the major current challenges and future opportunities are discussed. Several important battery challenges are likely to benefit from these in situ/operando techniques, including the inhomogeneous reactions of high-energy-density cathodes, the development of safe and reversible Li metal plating, and the development of stable SEI.

Through a facile sodium sulfide (Na₂S)-assisted hydrothermal treatment, clean and nondefective surfaces are constructed on micrometer-sized Li₄Ti₅O₁₂ particles. The remarkable improvement of surface quality shows a higher first cycle Coulombic efficiency (≈95%), a significantly enhanced cycling performance, and a better rate capability in electrochemical measurements. A combined study of Raman spectroscopy and inductive coupled plasma emission spectroscopy reveals that the evolution of Li₄Ti₅O₁₂ surface in a water-based hydrothermal environment is a hydrolysis–recrystallization process, which can introduce a new phase of anatase-TiO₂. While, with a small amount of Na₂S (0.004 mol L⁻¹ at least), the spinel-Li₄Ti₅O₁₂ phase is maintained without a second phase. During this process, the alkaline environment created by Na₂S and the surface adsorption of the sulfur-containing group (HS⁻ or S²⁻) can suppress the recrystallization of anatase-TiO₂ and renew the particle surfaces. This finding gives a better understanding of the surface–property relationship on Li₄Ti₅O₁₂ and guidance on preparation and modification of electrode material other than coating or doping.