Polymer-Garnet-Based Composite Cathodes for Solid-State Li Batteries

All-solid-state lithium batteries (ASSLBs) can potentially outperform conventional Li-ion batteries with liquid or polymer electrolyte. One example for solid electrolytes is the garnet-type oxide Li 7 La 3 Zr 2 O 12 (LLZO). LLZO has a wide electrochemical window, stability vs. lithium, and good ionic conductivity at room temperature. The cathode in ASSLBs is manufactured from a cathode active material (CAM), such as LiCoO 2 (LCO). The efficiency of Li-ion storage can be improved by the use of a composite cathode consisting from a CAM and an ion-conducting ceramic, e.g. LCO/LLZO. In such a composite cathode, LLZO delivers Li-ions through the whole bulk enhancing the volumetric loading of LCO. In this work the addition of polymer electrolyte into LCO/LLZO composite cathode was proposed, aiming at further increase of cell performance due to facilitation of CAM usage, similar to the approach of manufacturing of polymer-ceramic electrolytes. They are fabricated mostly by tape casting of slurry with polymer matrix, ceramic filler and a solvent. An alternative technology includes free sintering of tape-casted LCO/LLZO porous network and subsequent infiltration by liquid or polymer electrolyte. Free sintering of LCO/LLZO composite requires relatively high temperature and/or long sintering time. This results in loss of volatile Li with decrease in electrochemical performance. In the present work the LCO/LLZO composite cathode was manufactured in a powder-based process by Field-Assisted Sintering Technique also known as Spark Plasma Sintering (FAST/SPS). Fast heating (100°C/min and higher) and application of mechanical pressure during FAST/SPS enable reduction of sintering temperature and processing time needed for fabrication of nearly-fully-dense composite.[1] Thereby, Li evaporation and grain growth can be significantly reduced. This technology was used in our previous work for fabrication of half-cells with dense LLZO electrolyte and dense LCO/LLZO composite cathode. However, the appearance of side phase after sintering at low pressure and a residual porosity was observed. The reason for that was partial reduction of oxides by carbon originated from graphite foil in FAST/SPS setup. In the presented work, the graphite foil was replaced by carbon-free mica foil. This measure enabled FAST/SPS sintering of porous LCO/LLZO network without side phase formation. The obtained porous skeleton was infiltrated with polymer electrolyte to fabricate a polymer-ceramic composite cathode. The cathode was assembled with an anodic half-cell consisting of dense FAST/SPS-sintered LLZO electrolyte and attached indium (In) foil used as anode. The ASSLB with polymer-ceramic composite cathode showed significantly lower interfacial impedance and remarkably higher area-specific storage capacity as compared to the similar ASSLBs with pure ceramic (porous or dense) composite cathodes. Thus, the functionality and the advanced storage capacity of the proposed polymer-ceramic cathode and related ASSLB architecture were demonstrated.[2] References: [1] M. Ihrig, M. Finsterbusch, C.-L. Tsai, A.M. Laptev, C.-h. Tu, M. Bram, Y.J. Sohn, R. Ye, S. Sevinc, S.-k. Lin, D. Fattakhova-Rohlfing, O. Guillon, Journal of Power Sources, 482 (2021) 228905. [2] M. Ihrig, R. Ye, A.M. Laptev, D. Grüner, R. Guerdelli, W.S. Scheld, M. Finsterbusch, H.-D. Wiemhöfer, D. Fattakhova-Rohlfing, O. Guillon, ACS Applied Energy Materials, 4 (2021) 10428-10432. Figure 1