Decoupled Synthesis Pathway via Precursor Functionalization Stabilizes High-Voltage Nickel-Based Cathodes.

Nickel-based layered cathodes are promising candidates for high-performance, high-energy lithium-ion batteries, yet their high-voltage application is jointly limited by synthesis-inherited structural defects and an unstable lattice oxygen framework. Here, we show that both limitations can be overcome by decoupled synthesis pathway (DSP) via La/Nb oxalate functionalization of the Ni0.6Co0.1Mn0.3(OH)2 precursor. Unlike the conventional coupled synthesis pathway (CSP) where precursor dehydration and Li2CO3 decomposition overlap in temperature, the DSP introduces a low‑temperature decomposition of La/Nb oxalates at 200°C, which effectively avoids localized contact between the precursor and Li2CO3 and shifts Li2CO3-related reactions to high temperatures. This allows sequential precursor dehydroxylation, rock‑salt (RS) intermediate formation, and layered‑phase transformation over a broad temperature window. The resulting LiNi0.6Co0.1Mn0.3O2 cathode with La/Nb functionalization (NCM-LN) features a uniform surface LaNiO3 perovskite heterostructure and a Nb‑doped layered bulk with suppressed RS and spinel defects. Consequently, under 4.5 V operation (vs. Li+/Li), NCM-LN exhibits homogeneous Li+ (de)intercalation, and a stabilized oxygen framework. In graphite||NCM-LN full cells, NCM-LN retains 80.1% of its capacity after 2000 cycles at 1C, substantially outperforming the pristine cathode. This decoupling strategy is broadly effective across various Ni‑based systems, providing a generalizable route toward high‑energy, long‑life cathode materials.