Surface Li+/H+ Exchange Engineering for Enhancing Structural Stability and Electrochemical Performance of Lithium-Rich Manganese-Based Layered Oxides

Jinzhen Hu; Bingchen Wu; Feng Wang; Hui Guo; Jihuan Xie; Xueyi Sun; Junhang Tian; Nuria Tapia-Ruiz; Weidong Zhuang

doi:10.1002/smll.202509446

Surface Li⁺/H⁺ Exchange Engineering for Enhancing Structural Stability and Electrochemical Performance of Lithium-Rich Manganese-Based Layered Oxides

Small. 2025 Nov 6:e09446. doi: 10.1002/smll.202509446. Online ahead of print.

Authors

Jinzhen Hu^{1

2

3}, Bingchen Wu^{4

5}, Feng Wang^{1

2

3}, Hui Guo^{1

2

3}, Jihuan Xie^{1

2

3}, Xueyi Sun^{1

2

3}, Junhang Tian^{1

2

3}, Nuria Tapia-Ruiz^{4

5}, Weidong Zhuang^{1

2

3}

Affiliations

¹ State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing, 100083, China.
² School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, 100083, China.
³ Beijing Key Laboratory of Green Recovery and Extraction of Rare and Precious Metals, University of Science and Technology Beijing, Beijing, 100083, China.
⁴ Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, London, W12 0BZ, UK.
⁵ The Faraday Institution, Quad One, Harwell Science and Innovation Campus, Didcot, OX11 0RA, UK.

PMID: 41195649
DOI: 10.1002/smll.202509446

Abstract

Lithium-rich manganese-based layered oxides (LRO) are promising ultra-high-capacity cathode materials for next-generation lithium-ion batteries but suffer from structural instability, capacity/voltage decay, and poor rate capability. Herein, a novel surface spinel coating strategy is proposed to address these challenges through a citric acid solution treatment followed by thermal annealing. A Li₄Mn₅O₁₂ spinel coating layer is formed on the cathode material surface via Li⁺/H⁺ exchange and structural rearrangement, while preserving the bulk-layered structure. The spinel phase not only suppresses interfacial side reactions and lattice oxygen loss but also establishes 3D Li⁺ diffusion channels, enhancing kinetics and surface stability. The modified cathode material exhibits remarkable electrochemical improvements with a high-rate capacity of 205.29 mAh g^-1 at 5 C, and 86.3% capacity retention after 150 cycles at 1 C, outperforming the untreated LRO. This work provides a scalable surface engineering approach to reconcile the trade-off between high energy density and long-cycle stability in the LRO, advancing their practical viability for high-energy-density batteries.

Keywords: Li+/H+ exchange; citric acid; lithium‐rich manganese‐based oxides; side reactions; spinel coating.