Decoupled Synthesis Pathway via Precursor Functionalization Stabilizes High-Voltage Nickel-Based Cathodes.
basic_science · Level V
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- Record sourced from PubMed, PMID 42700441.
- Also identified by DOI 10.1002/adma.74909.
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Abstract
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 Ni<sub>0.6</sub>Co<sub>0.1</sub>Mn<sub>0.3</sub>(OH)<sub>2</sub> precursor. Unlike the conventional coupled synthesis pathway (CSP) where precursor dehydration and Li<sub>2</sub>CO<sub>3</sub> 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 Li<sub>2</sub>CO<sub>3</sub> and shifts Li<sub>2</sub>CO<sub>3</sub>-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 LiNi<sub>0.6</sub>Co<sub>0.1</sub>Mn<sub>0.3</sub>O<sub>2</sub> cathode with La/Nb functionalization (NCM-LN) features a uniform surface LaNiO<sub>3</sub> perovskite heterostructure and a Nb‑doped layered bulk with suppressed RS and spinel defects. Consequently, under 4.5 V operation (vs. Li<sup>+</sup>/Li), NCM-LN exhibits homogeneous Li<sup>+</sup> (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.