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.

Surface degradation is a common challenge for many electrode materials. The active surface usually reacts with the molecules in the surrounding environment to form byproducts that hinder the diffusion channels for Li ions and electrons, increase the energy barrier for (de)lithiation reactions, and ultimately shorten the cycle life. Herein, the growth of surface Li ₂ CO ₃ on LiNi _x Co _y Mn _y O ₂ (x = 0.33, 0.6, 0.7, 0.8, x + 2y = 1) cathodes upon storage has been systematically investigated. Ni-rich surfaces are found to result in more Li ₂ CO ₃ growth, based on which three discrete degradation models for layered oxides are proposed. The increase and discretization of the energy barrier for individual particles also explain the State-of-Charge heterogeneity phenomena observed by in situ XRD and the change of cyclic voltammetry curves. By providing a comprehensive picture of surface deterioration of the NCM cathode family, this study enhances the understanding of the degradation mechanism that determines the cycle life of electrode materials.

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.