All-solid-state lithium batteries are poised to become the forefront of high-performance energy storage and power solutions. The cornerstone of their development lies in crafting exceptional solid-state electrolytes that not only exhibit superior ion transport capabilities and a broad electrochemical window but also effectively mitigate lithium dendrite growth, thereby averting battery short circuits. The lithium-ion conductivity of these electrolytes is intricately tied to their chemical milieu and transport pathways, ideally approaching or even surpassing that of liquid electrolytes. Polymer electrolytes, exemplified by polyethylene oxide (PEO), mimic liquid-like ion transport properties but suffer from low ionic conductivity and transference numbers due to sluggish segmental mobility. Conversely, inorganic crystalline electrolytes offer swift ion transport and high transference numbers but grapple with poor interface contact and lattice periodicity-constrained ion transport.