Good safety, high interfacial compatibility, low cost, and facile processability make polymer‐based solid electrolytes promising materials for next‐generation batteries. Key issues related to polymer‐based solid electrolytes, such as synthesis methods, ionic conductivity, and battery architecture, are investigated in past decades. However, mechanistic understanding of the ionic conduction is still lacking, which impedes the design and optimization of polymer‐based solid electrolytes. In this review, the ionic conduction mechanisms and optimization strategies of polymer‐based solid electrolytes, including solvent‐free polymer electrolytes, composite polymer electrolytes, and quasi‐solid/gel polymer electrolytes, are summarized and evaluated. Challenges and strategies for enhancing the ionic conductivity are elaborated, while the ion‐pair dissociation, ion mobility, polymer relaxation, and interactions at polymer/filler interfaces are highlighted. This comprehensive review is especially pertinent for the targeted enhancement of the Li‐ion conductivity of polymer‐based solid electrolytes.

Solid electrolytes hold the promise for enabling high-performance lithium (Li) metal batteries, but suffer from Li-filament penetration issues. The mechanism of this rate-dependent failure, especially the impact of the electrochemo-mechanical attack from Li deposition, remains elusive. Herein, we reveal the Li deposition dynamics and associated failure mechanism of solid electrolyte by visualizing the Li|Li7La3Zr2O12 (LLZO) interface evolution via in situ transmission electron microscopy (TEM). Under a strong mechanical constraint and low charging rate, the Li-deposition-induced stress enables the single-crystal Li to laterally expand on LLZO. However, upon Li “eruption”, the rapidly built-up local stress, reaching at least GPa level, can even crack single-crystal LLZO particles without apparent defects. In comparison, Li vertical growth by weakening the mechanical constraint can boost the local current density up to A·cm−2 level without damaging LLZO. Our results demonstrate that the crack initiation at the Li|LLZO interface depends strongly on not only the local current density but also the way and efficiency of mass/stress release. Finally, potential strategies enabling fast Li transport and stress relaxation at the interface are proposed for promoting the rate capability of solid electrolytes.

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Solid-electrolyte interface (SEI) is "the most important but least understood (component) in rechargeable Liion batteries". The ideal SEI requires high elastic strength and can resist the penetration of a Li dendrite mechanically, which is vital for inhibiting the dendrite growth in lithium batteries. Even though Li 2 CO 3 and Li 2 O are identified as the major components of SEI, their mechanical properties are not well understood. Herein, SEIrelated materials such as Li 2 CO 3 and Li 2 O were electrochemically deposited using an environmental transmission electron microscopy (ETEM), and their mechanical properties were assessed by in situ atomic force microscopy (AFM) and inverse finite element simulations. Both Li 2 CO 3 and Li 2 O exhibit nanocrystalline structures and good plasticity. The ultimate strength of Li 2 CO 3 ranges from 192 to 330 MPa, while that of Li 2 O is less than 100 MPa. These results provide a new understanding of the SEI and its related dendritic problems in lithium batteries. KEYWORDS: Li 2 CO 3 and Li 2 O, mechanical properties, in situ environmental transmission electron microscopy (ETEM), atomic force microscopy (AFM), finite element simulations

The mechanisms of Li deposition behaviors, which overwhelmingly affect battery performances and safety, are far to be understood in solid-state batteries. Here, using in situ micro-nano electrochemical scanning electron microscopy (SEM) manipulation platform, dynamic Li plating behaviors on 10 metallic substrates have been tracked, and the underlying mechanisms for dendrite-free Li plating are elucidated. Distinct Li deposition behaviors on Cu, Ti, Ni, Bi, Cr, In, Ag, Au, Pd, and Al are revealed quantitatively in nucleation densities, growth rates, and anisotropic ratios. For Li alloyable metals, the dynamic Li alloying process before Li growth is visually captured. It is concluded that a good affinity for Li and appropriate lattice compatibility between the substrate and Li are needed to facilitate homogeneous Li plating. Our work not only uncovers the Li plating dynamics, shedding light on the design of solid-state batteries, but also provides a powerful integrated SEM platform for future in-depth investigation of solid-state batteries.