Lithium‐ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage‐induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and over‐discharge, while temperature‐induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

Smart electronics and wearable devices require batteries with increased energy density, enhanced safety, and improved mechanical flexibility. However, current state‐of‐the‐art Li‐based rechargeable batteries (LBRBs) use highly reactive and flowable liquid electrolytes, severely limiting their ability to meet the above requirements. Therefore, solid polymer electrolytes (SPEs) are introduced to tackle the issues of liquid electrolytes. Nevertheless, due to their low Li⁺ conductivity and Li⁺ transference number (LITN) (around 10⁻⁵ S cm⁻¹ and 0.5, respectively), SPE‐based room temperature LBRBs are still in their early stages of development. This paper reviews the principles of Li⁺ conduction inside SPEs and the corresponding strategies to improve the Li⁺ conductivity and LITN of SPEs. Some representative applications of SPEs in high‐energy density, safe, and flexible LBRBs are then introduced and prospected.

Low temperatures severely impair the performance of lithium-ion batteries, which demand powerful electrolytes with wide liquidity ranges, facilitated ion diffusion, and lower desolvation energy. The keys lie in establishing mild interactions between Li⁺ and solvent molecules internally, which are hard to achieve in commercial ethylene-carbonate based electrolytes. Herein, we tailor the solvation structure with low-ε solvent-dominated coordination, and unlock ethylene-carbonate via electronegativity regulation of carbonyl oxygen. The modified electrolyte exhibits high ion conductivity (1.46 mS·cm⁻¹) at −90 °C, and remains liquid at −110 °C. Consequently, 4.5 V graphite-based pouch cells achieve ~98% capacity over 200 cycles at −10 °C without lithium dendrite. These cells also retain ~60% of their room-temperature discharge capacity at −70 °C, and miraculously retain discharge functionality even at ~−100 °C after being fully charged at 25 °C. This strategy of disrupting solvation dominance of ethylene-carbonate through molecular charge engineering, opens new avenues for advanced electrolyte design.