All-solid-state lithium-ion batteries (ASSLIBs) with oxide-based solid electrolytes are a promising candidate for next generation of rechargeable batteries, due to their reliability and high-energy density. The formation of well-defined electrode/solid electrolyte interfaces with an excellent ionic conductivity by co-sintering is one of the key challenges to develop oxide-based ASSLIBs.¹ Electrode materials and solid electrolytes often react with each other to form a resistive substance at their interface during co-sintering.^2-4 Thus, optimization of the co-sintering conditions is important to control the interfacial structure which governs the ionic conductivity. However, the effect of the interfacial structure on the ionic conductivity remains unclear.

In this study, we co-sintered the composites of LiCoPO₄ (LCP) electrode material and Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) oxide-based solid electrolyte and investigated the interfacial structure by using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and scanning transmission electron microscopy combined with electron energy loss spectroscopy and an energy-dispersive X-ray spectroscopy (STEM-EELS/EDX).

Figure 1(a) shows the XRD patterns of the LCP/LATP composites before and after sintering at 800°C. The diffraction patterns are almost identical to each other and all the diffraction peaks are attributed to the LCP and LATP with an exception of AlPO₄ impurity. However, the Co K-edge XANES is slightly changed after sintering as shown in Figure 1(b). These results suggest that a small amount of LCP and LATP react with each other. Figure 1(c) shows a typical STEM image of the LCP/LATP composites after sintering at 800°C. According to EDX analysis, light and dark gray domains correspond to LCP and LATP, respectively. Apart from LCP and LATP, there are two types of LCP/LATP interfaces: interface A and B. Line profile STEM-EELS/EDX analysis revealed that LCP and LATP directly bound to each other at the interface A. On the other hand, a thermally reacted thin layer, possibly cobalt oxide (CoO) and/or cobalt phosphide (Co₂P), is formed at interface B. The effect of such thermally reacted interlayer on the ionic conductivity will be discussed in detail.

References:

1. R. Chen, Q. Li, X. Yu, L. Chen and H. Li, Chemical Reviews, 2020, 120, 6820-6877.
2. M. Gellert, E. Dashjav, D. Grüner, Q. Ma and F. Tietz, Ionics, 2017, 24, 1001-1006.
3. C.-Y. Yu, J. Choi, V. Anandan and J.-H. Kim, The Journal of Physical Chemistry C, 2020, 124, 14963-14971.
4. L. Miara, A. Windmuller, C. L. Tsai, W. D. Richards, Q. Ma, S. Uhlenbruck, O. Guillon and G. Ceder, ACS Applied Materials and Interfaces, 2016, 8, 26842-26850.