Low‐Temperature Flexible Integration of All‐Solid‐State Thin‐Film Lithium Batteries Enabled by Spin‐Coating Electrode Architecture

Abstract Micro energy sources as the nucleus of intelligent microdevices guarantee their full autonomy in the dimensions of time and space. However, the state‐of‐the‐art micro energy storage components, like all‐solid‐state thin‐film microbatteries (ASSTFBs), whose direct integration is impeded by the stereotyped vacuum‐based manufacturing technologies, for which an inevitable high‐temperature annealing step (> 500 °C) can exert catastrophic effects on the attached microdevices during the crystallization of manufactured insertion thin‐film cathodes, especially in flexible integration. Herein, a prototype construction is created to benchmark concrete feasibility for the low‐temperature manufacturing of ASSTFBs via a nonvacuum‐based spin‐coating electrode architecture. Results show that the spin‐coated LiFePO 4 films enable low‐temperature (≈ 45 °C) manufacturing of ASSTFBs, by which it can deliver excellent cycling performance up to 1000 cycles. Importantly, this technology presents the versatility of integrating various cathode composites into ASSTFBs and is therefore generalized to the LiCoO 2 ‐ and Li 4 Ti 5 O 12 ‐based solid‐state chemistries. Furthermore, ASSTFBs with such compliant electrodes manifest outstanding flexibility without pronounced capacity degradation by successfully integrating on flexible temperature‐sensitive substrates. The spin‐coating protocol provides a general solution for excessive processing temperatures and ample opportunities for the development of on‐chip integratable and flexible ASSTFBs.