All-solid-state lithium-ion batteries (ASLBs) are receiving considerable attention due to their safety superiority and high energy density (achieved by bipolar configuration). Inorganic solid electrolytes are explored as a key-enabling material of the ASLBs. However, their critical challenges, including grain boundary resistance, interfacial instability with electrode materials and complicated processability, remain yet unresolved. Here, we demonstrate a new class of gel electrolyte with reversible thixotropic transformation and abuse tolerance as an effective and scalable approach to address the aforementioned longstanding issues. The gel electrolyte consists of (fluoropolymer/cellulose derivative) matrix and liquid electrolyte. The reversible thixotropic transformation is realized via sol-gel transition based on Coulombic interaction of the polymer matrix with liquid electrolyte. This unusual rheological feature allows the gel electrolyte to be printed in various forms. In addition, the gel electrolyte shows low crystallinity, thus playing a viable role in delivering high ionic conductivity. Based on understanding of rheological/electrochemical characteristics of the gel electrolyte, we fabricate a form factor-free pouch-type cell assembled with the gel electrolyte using sequential screen-printing process. The resultant cell shows exceptional safety upon exposure to various harsh abuse conditions, along with decent electrochemical performance.

全固态锂离子电池（ASLB）由于其安全性优越和高能量密度（通过双极配置实现）而受到了广泛关注。无机固体电解质被认为是ASLBs的关键材料。然而，它们的关键挑战，包括晶界电阻，与电极材料的界面不稳定性以及复杂的可加工性，仍未解决。在这里，我们展示了具有可逆触变性和耐滥用性的新型凝胶电解质，作为解决上述长期存在问题的有效且可扩展的方法。凝胶电解质由（含氟聚合物/纤维素衍生物）基质和液体电解质组成。通过基于聚合物基质与液体电解质的库仑相互作用的溶胶-凝胶转变来实现可逆触变转变。这种不寻常的流变特性使凝胶电解质可以各种形式印刷。另外，凝胶电解质显示出低结晶度，因此在传递高离子电导率方面起着可行的作用。基于对凝胶电解质的流变/电化学特性的了解，我们使用顺序的丝网印刷工艺制造了与凝胶电解质组装在一起的无形状因子的袋型电池。所得到的电池在各种恶劣的使用条件下显示出卓越的安全性，并具有良好的电化学性能。另外，凝胶电解质显示出低结晶度，因此在传递高离子电导率方面起着可行的作用。基于对凝胶电解质的流变/电化学特性的了解，我们使用顺序的丝网印刷工艺制造了与凝胶电解质组装在一起的无形状因子的袋型电池。所得到的电池在各种恶劣的恶劣条件下显示出卓越的安全性，并具有良好的电化学性能。另外，凝胶电解质显示出低结晶度，因此在传递高离子电导率方面起着可行的作用。基于对凝胶电解质的流变/电化学特性的了解，我们使用顺序的丝网印刷工艺制造了与凝胶电解质组装在一起的无形状因子的袋型电池。所得到的电池在各种恶劣的恶劣条件下显示出卓越的安全性，并具有良好的电化学性能。