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Tuning Li/Ni mixing by reactive coating to boost the stability of cobalt-free Ni-rich cathode 被引量:1

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摘要 Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.
出处 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第10期20-29,I0002,共11页 能源化学(英文版)
基金 financial support from the Natural Science Foundation of Shandong Province (ZR2022QB140) the PhD Initiation Program of Liaocheng University (318052138) the Natural Science Foundation of Shandong Province (ZR2023MB002 and ZR2021MB114)。
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