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<p>The widespread adoption of LiFePO<sub>4</sub> as a cathode material is hindered by its intrinsically low ionic and electronic conductivity. While transition metal doping is a recognized strategy to mitigate these limitations, the precise mechanistic underpinnings remain elusive. Here, we present a comprehensive multi-scale investigation into copper-doped LiFePO<sub>4</sub> (LiCu<sub><i>x</i></sub>Fe<sub>1−<i>x</i></sub>PO<sub>4</sub>) that not only demonstrates a dramatic enhancement in performance but also uncovers the fundamental role of local structural disorder. Our study, which integrates advanced synchrotron-based characterizations including X-ray pair distribution function (PDF) analysis, and X-ray absorption spectroscopy (XAS) with Raman spectroscopy, electrochemical analysis, and molecular dynamics simulations, reveals a compelling structure-property relationship. We show that despite a negligible change in the average crystal structure, Cu doping induces significant local structural disorder. This effect is directly responsible for a remarkable enhancement in lithium-ion diffusion by nearly two orders of magnitude and a staggering six-fold increase in specific capacity for the optimal doping concentration (x=0.05) compared to the undoped material. Our molecular dynamics simulations further provides qualitative understanding on how the local disorder significantly lowers the energy barriers for Li-ion migration. This work offers microscopic insights, establishing the local structural disorder as a critical enabler of superior cathode kinetics and providing a new paradigm for designing high-performance electrochemical materials.</p>

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Enhanced kinetics in Cu-doped LiFePO4 cathodes due to local structural disorder

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月7日

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  • Dharmendra Kumar,
  • A. Tripathy,
  • Manju Sharma,
  • S. R. Sahu,
  • Samanway Mohanta,
  • Ashutosh Anand,
  • Sreejith O. V,
  • Ramaswamy Murugan,
  • Sanjay Singh,
  • Rajamani Raghunathan,
  • V. G. Sathe,
  • Surender Kumar Sharma,
  • D. K. Shukla

摘要

The widespread adoption of LiFePO4 as a cathode material is hindered by its intrinsically low ionic and electronic conductivity. While transition metal doping is a recognized strategy to mitigate these limitations, the precise mechanistic underpinnings remain elusive. Here, we present a comprehensive multi-scale investigation into copper-doped LiFePO4 (LiCuxFe1−xPO4) that not only demonstrates a dramatic enhancement in performance but also uncovers the fundamental role of local structural disorder. Our study, which integrates advanced synchrotron-based characterizations including X-ray pair distribution function (PDF) analysis, and X-ray absorption spectroscopy (XAS) with Raman spectroscopy, electrochemical analysis, and molecular dynamics simulations, reveals a compelling structure-property relationship. We show that despite a negligible change in the average crystal structure, Cu doping induces significant local structural disorder. This effect is directly responsible for a remarkable enhancement in lithium-ion diffusion by nearly two orders of magnitude and a staggering six-fold increase in specific capacity for the optimal doping concentration (x=0.05) compared to the undoped material. Our molecular dynamics simulations further provides qualitative understanding on how the local disorder significantly lowers the energy barriers for Li-ion migration. This work offers microscopic insights, establishing the local structural disorder as a critical enabler of superior cathode kinetics and providing a new paradigm for designing high-performance electrochemical materials.