# Boosting Li+ Diffusion in Lithium-Rich Oxides through Intrinsic Structural Design: Insights and Design Principles

## TL;DR

This paper explores how to improve lithium-ion transport in lithium-rich oxides to enhance battery performance through structural design and advanced analysis.

## Contribution

The paper provides design principles and mechanistic insights for boosting Li+ diffusion in lithium-rich oxides via intrinsic structural optimization.

## Key findings

- Lattice distortion and oxygen redox chemistry significantly modulate Li+ pathways and energy barriers.
- Interface engineering and morphology-directed design improve ionic diffusivity in lithium-rich oxides.
- Advanced operando techniques are essential for analyzing dynamic structural and chemical evolution in these materials.

## Abstract

Sluggish Li+ transport limits high-power output and fast charging in lithium-rich oxides, governed by intrinsic factors (crystal structure, distortion, and reaction kinetics) and external factors (cathode/electrolyte interface behavior, volumetric strain, and particle size distribution).Rate performance can be improved through interface engineering, targeted doping, particle morphology control, bulk structural optimization, and manipulation of redox chemistry to accelerate Li+ transport and stabilize electrochemical reactions.Understanding dynamic Li+ transport requires advanced operando characterization and multiscale computational modeling. Overcoming the capacity-kinetics paradox requires a mechanism-driven approach aimed at lowering the energy barriers for Li+ migration.

Sluggish Li+ transport limits high-power output and fast charging in lithium-rich oxides, governed by intrinsic factors (crystal structure, distortion, and reaction kinetics) and external factors (cathode/electrolyte interface behavior, volumetric strain, and particle size distribution).

Rate performance can be improved through interface engineering, targeted doping, particle morphology control, bulk structural optimization, and manipulation of redox chemistry to accelerate Li+ transport and stabilize electrochemical reactions.

Understanding dynamic Li+ transport requires advanced operando characterization and multiscale computational modeling. Overcoming the capacity-kinetics paradox requires a mechanism-driven approach aimed at lowering the energy barriers for Li+ migration.

Lithium-rich oxide cathodes present high specific capacities (> 250 mAh g−1) and wide operating voltage windows (2.0–4.8 V), making them promising candidates for next-generation high-energy batteries. Their practical deployment, however, is limited by sluggish ion transport kinetics that arise from inherent structural constraints, including confined two-dimensional diffusion channels, transition metal migration, and local lattice distortions. These structural perturbations narrow Li+ pathways, intensify cation mixing, and generate localized strain fields, collectively increasing the Li+ migration energy barrier. To facilitate the rational design of fast-kinetic lithium-rich oxides through intrinsic structural optimization, a comprehensive elucidation of the structure–diffusion interplay is presented, with emphasis on the roles of lattice distortion and oxygen redox chemistry in modulating Li+ pathways and associated energy barriers. Structural design strategies that aim to improve ionic diffusivity are systematically evaluated, including interface engineering, morphology-directed design, and the modulation of redox chemistry. Advanced operando characterization techniques that capture dynamic structural and chemical evolution are also described as essential tools for guiding precise structure–performance analysis. The mechanistic insights and integrated analytical approaches summarized in this review establish a robust conceptual foundation for engineering lithium-rich oxides with enhanced ion transport kinetics, thereby supporting the advancement of next-generation high-power battery technologies.