Study on the Structural Degradation of the Polyaniline(PANi) Coated LiNi0.90Co0.85Mn0.15o Particles

Abstract

The nickel content of the layered lithium transition metal oxide cathodes is proportional to the discharge capacity of energy storage systems. Ni2+ ion, the oxidation state of Ni, moves to the Li sites when Li+ ion is deintercalated during discharge process due to the similar size of ion (Ni2+: 0.069 nm, Li+: 0.076 nm). The spatial transition of Ni2+ ion causes gradual cation mixing and structure degradation of cathode, resulting in the failure of the battery. Also, thick cathode-electrolyte interphase (CEI) is formed on the cathode surface because of the transition metal dissolution, the degradation of electrolyte, and the residual gas such as H2O and CO2.Coating technology is one of the strategies for the physical protection of the cathode surface and the control of CEI layer thickness. Polyaniline(PANi) is a conductive polymer with stable oxidation state. PANi can enhance the electrochemical property and structural stability as a protective layer. In this study, we synthesized PANi material by the oxidative polymereization and coated NCM with the synthesized PANi by sonication method.The PANi-coated NCM(PANi@NCM) has uniform coating layer with 5 nm thickness. PANi@NCM exhibits an initial discharge capacity of 208 mAhg-1 and a capacity retention of 81% after 50 cycles at 45 oC in Figure 1(a) and (b). After the cycling test, pristine and coated cathodes were disassembled for the comparison of the microstructure. Pristine NCM only shows the structural transition from layered structure to structure in the XRD pattern of Figure 1(c). Cross-sectional SEM image of the pristine NCM after cycling test shows micro and macro cracks are distributed from the bulk to the surface of the cathode as shown in Figure 1(d). On the other side, cracks are barely observed on the PANi@NCM particles in Figure 1(e). The layered structure of PANi@NCM is maintained even after cycling test, which are confirmed by TEM analysis with FFT patterns and HAADF images. Figure (f) and (g) show the FFT pattern of the two cathode surfaces after cycling test. Mixed phase is observed on the pristine cathode surface, while the layered structure is maintained on the PANi@NCM surface. Also, the PANi@NCM maintains a thinner passivation layer compared with that of the pristine NCM (6 nm vs 35 nm). In conclusion, the PANi coating layer prevents the degradation of structure and the formation of thick CEI layer. The structural stability enhances the electrochemical performance. Figure 1