RESUMO
Ni-rich layered oxides have received significant attention as promising cathode materials for Li-ion batteries due to their high reversible capacity. However, intergranular and intragranular cracks form at high state-of-charge (SOC) levels exceeding 4.2 V (vs. Li/Li+), representing a prominent failure mechanism of Ni-rich layered oxides. The nanoscale crack formation at high SOC levels is attributed to a significant volume change resulting from a phase transition between the H2 and H3 phases. Herein, in contrast to the electrochemical crack formation at high SOC levels, another mechanism of chemical crack and pit formation on a nanoscale is directly evidenced in fully lithiated Ni-rich layered oxides (low SOC levels). This mechanism is associated with intergranular stress corrosion cracking, driven by chemical corrosion at elevated temperatures. The nanoscopic chemical corrosion behavior of Ni-rich layered oxides during aging at elevated temperatures is investigated using high-resolution transmission electron microscopy, revealing that microcracks can develop through two distinct mechanisms: electrochemical cycling and chemical corrosion. Notably, chemical corrosion cracks can occur even in a fully discharged state (low SOC levels), whereas electrochemical cracks are observed only at high SOC levels. This finding provides a comprehensive understanding of the complex failure mechanisms of Ni-rich layered oxides and provides an opportunity to improve their electrochemical performance.
RESUMO
Interphase engineering is becoming increasingly important in improving the electrochemical performance of cathode materials for rechargeable batteries, including Li ion, Li metal, and all-solid-state batteries, because irreversible surface reactions, such as electrolyte decomposition, and transition metal dissolution, constitute one of these batteries' failure modes. In this connection, various surface-engineered cathode materials have been investigated to improve interfacial properties. No synthesis methods, however, have considered a plane-selective surface modification of cathode materials. Herein, we introduce the basal-plane-selective coating of Li2SnO3 on layered Li[NixCo1-x]O2 (x = 0 and 0.5) using the concept of the thermal phase segregation of Sn-doped Li[NixCo1-x]O2 due to the solubility variation of Sn in Li[NixCo1-x]O2 with respect to temperature. The plane-selective surface modification enables the formation of Li2SnO3 nanolayers on only the Li[NixCo1-x]O2 basal plane without hindering the charge transfer of Li+ ions. As a result, the vertical heterostructure of Li[NixCo1-x]O2-Li2SnO3 core-shells show promising electrochemical performance.