Elucidating the mechanism of microscopic conduction in cathode composites for all-solid-state batteries through scanning spreading resistance microscopy

Abstract

The microstructure design of electrodes comprising active materials and solid electrolytes (SE) determines the conduction properties of the electrode composites and the overall battery performance of all-solid-state batteries (ASSBs). This correlation, which is generally evaluated using macroscopic parameters based on effective conductivity, can be understood through insights into the microscopic conduction mechanism. Here, we investigate the microscopic electronic conduction properties of LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) cathode composites employed in ASSBs using scanning spreading resistance microscopy (SSRM). The cathode composites with low NCM volume fractions show a bimodal resistance distribution in the NCM domains, leading to capacity deficit due to sparse electronic conductive networks. A simulation of the 3D microstructure generated by machine learning suggests that the resistance component of the composite detected using SSRM is strongly influenced by the electronic contact resistance between the material directly beneath the probe and other materials. Our findings emphasize that high electrochemical utilization of ASSBs requires minimization of the electronic contact resistance between the cathode active materials. The combination of SSRM and 3D generative microstructure simulation enables the evaluation of the electronic contact resistance between particles within inhomogeneous composites, such as ASSB electrodes. This approach provides fundamental guidelines for optimizing microstructure design to achieve high-performance ASSBs.