Citation: Yuhong Luo, Tian Chen, Yingde Huang, Peiyao Li, Yujing Chen, Zhenyu Wang, Qing Wu, Xiahui Zhang, Junchao Zheng. Quantifying the pillar effect of cations in ion-exchanged Ni-rich oxide cathodes for lithium-ion batteries[J]. Chinese Chemical Letters, ;2026, 37(12): 111700. doi: 10.1016/j.cclet.2025.111700 shu

Quantifying the pillar effect of cations in ion-exchanged Ni-rich oxide cathodes for lithium-ion batteries

Yuhong Luo ^{a, c} ,
Tian Chen ^{a, b} ,
Yingde Huang ^{a, b} ,
Peiyao Li ^{a, b} ,
Yujing Chen ^{a, b} ,
Zhenyu Wang ^{a, b} ,
Qing Wu ^d ,
Xiahui Zhang ^{a, b, *,} ,
Junchao Zheng ^{a, b, *,}

a.
School of Metallurgy and Environment, Central South University, Changsha 410083, China
b.
Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Central South University, Changsha 410083, China
c.
School of Chemistry, South China Normal University, Guangzhou 510006, China
d.
School of Information and Network Center Central South University, Changsha 410083, China

xhzhang@csu.edu.cn

jczheng@csu.edu.cn

Received Date: 15 May 2025
Revised Date: 5 August 2025
Accepted Date: 9 August 2025
Available Online: 10 August 2025

Figures(6)

Li⁺/Na⁺ ion exchange has made a breakthrough in the synthesis of Ni-rich layered cathode oxide, which can effectively mitigate the severe Li/Ni disorder that occurs in the traditional solid-phase sintering method. However, the comparative study of the cations presents in the Li layer as pillars is rarely reported. Herein, a series of Ni²⁺/Na⁺ co-substituted Ni-rich materials are designed by ion exchange at ∼200 °C with varying Li⁺/Na⁺ molar ratios (4, 8, 12, 16), which is used as a platform to quantitatively decipher the pillar effect contributed by Ni²⁺ and Na⁺ in the Li layer. We found that Ni²⁺ is approximately 3.5 times more effective as pillar than Na⁺. Theoretical calculations further reveal that Ni²⁺ in Li slab provides the higher mechanical strength than Na⁺ in the deeply delithiated state of Ni-rich materials. Besides, the results of structural evolution over cycling reveals that Ni²⁺ plays a greater role of pillar in stabilizing the structure with higher lattice energy compared to Na⁺, attributed to its higher mechanical strength (bulk modulus: 56.9 vs. 43.8 GPa). The PL-4 cathode (Li⁺/Na⁺ molar ratios = 4) exhibited optimal electrochemical performance, retaining 90.4% capacity after 70 cycles at 1 C and delivering a high specific capacity of 141.7 mAh/g at 10 C. This work provides design principles for the synthesis of layered oxides with high structural stability via ion exchange, potentially leading to the development of advanced cathode materials for high-energy lithium-ion batteries.
- Li⁺/Na⁺ ion exchange,
- Pillar effect,
- Ni-rich materials,
- Mechanical strength,
- Structural stability
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