Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries.

Chen, Ke; Barai, Pallab; Kahvecioglu, Ozgenur; Wu, Lijun; Pupek, Krzysztof Z; Ge, Mingyuan; Ma, Lu; Ehrlich, Steven N et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Lithium-ion batteries play a crucial role in decarbonizing transportation and power grids, but their reliance on high-cost, earth-scarce cobalt in the commonly employed high-energy layered Li(NiMnCo)O<sub>2</sub> cathodes raises supply-chain and sustainability concerns. Despite numerous attempts to address this challenge, eliminating Co from Li(NiMnCo)O<sub>2</sub> remains elusive, as doing so detrimentally affects its layering and cycling stability. Here, we report on the rational stoichiometry control in synthesizing Li-deficient composite-structured LiNi<sub>0.95</sub>Mn<sub>0.05</sub>O<sub>2</sub>, comprising intergrown layered and rocksalt phases, which outperforms traditional layered counterparts. Through multiscale-correlated experimental characterization and computational modeling on the calcination process, we unveil the role of Li-deficiency in suppressing the rocksalt-to-layered phase transformation and crystal growth, leading to small-sized composites with the desired low anisotropic lattice expansion/contraction during charging and discharging. As a consequence, Li-deficient LiNi<sub>0.95</sub>Mn<sub>0.05</sub>O<sub>2</sub> delivers 90% first-cycle Coulombic efficiency, 90% capacity retention, and close-to-zero voltage fade for 100 deep cycles, showing its potential as a Co-free cathode for sustainable Li-ion batteries.