Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism

Li, Danyang; Liu, Can; Zhao, Shu; Li, Fujie; Li, Hao; Wang, Chao; Zhao, Xiu Song

doi:10.3390/nano15120893

Open AccessArticle

Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism

by

Danyang Li

,

Can Liu

,

Shu Zhao

,

Fujie Li

,

Hao Li

,

Chao Wang

^*

and

Xiu Song Zhao

^*

Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China

^*

Authors to whom correspondence should be addressed.

Nanomaterials 2025, 15(12), 893; https://doi.org/10.3390/nano15120893

Submission received: 30 April 2025 / Revised: 6 June 2025 / Accepted: 8 June 2025 / Published: 10 June 2025

(This article belongs to the Section Energy and Catalysis)

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Abstract

Na-layered Li-containing Mn-based cathodes (Na_xLi_yMn_1-yO₂, NLMOs) with additional Na⁺ storage ability resulting from the anionic redox reaction (ARR) hold great promise for sodium-ion batteries (NIBs). However, practical applications of NLMOs encounter challenges, such as migration of transition metal Mn, loss of lattice oxygen, and voltage decay during cycling. Here, we show that Cu plays an important role in enhancing the ARR via the reductive coupling mechanism (RCM). Results shows that a Cu²⁺/Fe³⁺ modified NLMO sample delivers a Na⁺ storage capacity as high as 174 mA h g⁻¹ at 0.2C, higher than that of a Zn²⁺/Fe³⁺ modified NLMO sample (130 mA h g⁻¹) and NLMO (154 mA h g⁻¹). Both in situ and ex situ characterization results indicate that the obvious improvement in the electrochemical performance of the Cu²⁺/Fe³⁺ modified NLMO is due to the additional overlaps between the Cu 3d and O 2p orbitals, which is beneficial for the RCM. As a result, the ARR is enhanced so as to increase the Na⁺ storage capacity.

Keywords: sodium-ion battery; layered Mn-based oxide; anionic redox reaction; reductive coupling mechanism; elemental substitution

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MDPI and ACS Style

Li, D.; Liu, C.; Zhao, S.; Li, F.; Li, H.; Wang, C.; Zhao, X.S. Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism. Nanomaterials 2025, 15, 893. https://doi.org/10.3390/nano15120893

AMA Style

Li D, Liu C, Zhao S, Li F, Li H, Wang C, Zhao XS. Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism. Nanomaterials. 2025; 15(12):893. https://doi.org/10.3390/nano15120893

Chicago/Turabian Style

Li, Danyang, Can Liu, Shu Zhao, Fujie Li, Hao Li, Chao Wang, and Xiu Song Zhao. 2025. "Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism" Nanomaterials 15, no. 12: 893. https://doi.org/10.3390/nano15120893

APA Style

Li, D., Liu, C., Zhao, S., Li, F., Li, H., Wang, C., & Zhao, X. S. (2025). Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism. Nanomaterials, 15(12), 893. https://doi.org/10.3390/nano15120893

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Enhanced Anionic Redox Reaction of Na-Layered Li-Containing Mn-Based Cathodes by Cu-Mediated Reductive Coupling Mechanism

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