Electrode-to-electrode monolithic integration for high-voltage bipolar solid-state batteries based on plastic-crystal polymer electrolyte

Solid-state batteries (SSBs) offer a fundamental solution to mitigate the safety and reliability issues of conventional lithium-ion batteries utilizing flammable liquid electrolytes, and enable the bipolar configuration of high voltage and high-energy storage systems. However, the conventional layer-by-layer (LbL) stacking process using individual electrolyte and electrode layers suffers from poor electrolyte-electrode contacts and challenging process complications for manufacturing multi-layer bipolar SSBs. Herein, we report an electrode-to-electrode (EtE) monolithic integration without a free-standing solid electrolyte layer for high-voltage bipolar SSBs. Positive and negative electrodes seamlessly combined with a thin solid electrolyte are fabricated by the infusion of a plastic-crystal-based polymer electrolyte (PCPE) into porous electrodes with a subsequent ultraviolet-induced solidification process. The infused PCPE in the electrodes forms continuous Li+ conduction channels as well as intimate solid-solid interfaces. The thin PCPE film (-10 mu m) formed in situ on the top of the electrodes during the infusion process provides ultra-high Li+ conductance (-3.1 S cm(-2) at 45 ?) between the two electrodes. SSBs are constructed via direct integration of the PCPE-infused electrodes: a unit cell-type SSB with LiNi0.6-Co0.2Mn0.2O2 (positive) and Li4Ti5O12 (negative) show superior capacity (-160 mAh g(-1)), rate capability (98 mAh g(-1) at 2C), and stable cyclability (81% after 100 cycles) at 45 ? than the SSB fabricated by the conventional LbL stacking process. Moreover, a 10 V-class, bipolar SSB comprising five unit cells stacked in series is constructed via the EtE monolithic integration of multiple PCPE-infused bipolar electrodes, and its stable cycle performance is corroborated with a capacity retention of 84%. This work demonstrates that the suggested EtE integration process offers a promising strategy to addressing the interfacial contact issues of SSBs, thereby being utilized to realize scalable, low-cost, high-voltage bipolar SSBs.