Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage

Rechargeable aqueous zinc-ion batteries (AZIBs) have emerged as a leading contender for stationary energy storage systems due to their low cost, safety, and environmental sustainability. However, their widespread practical application is hindered by the limited stability and capacity of current AZIB...

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Detalles Bibliográficos
Autores: Chacón-Borrero, Jesús, Chang, Xingqi, Min, Zhiwen, Yu, Jing, Montaña-Mora, Guillem, Mejia-Centeno, Karol V., Sun, Yuanmiao, Zhou, Xiaolong, Tunmee, Sarayut, Kidkhunthod, Pinit, Li, Junshan, Llorca, Jordi, Arbiol, Jordi, Cabot, Andreu
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/399225
Acceso en línea:http://hdl.handle.net/10261/399225
https://api.elsevier.com/content/abstract/scopus_id/105012221915
Access Level:acceso abierto
Palabra clave:Binder-free
High-capacity retention
Self-supporting electrode
Zinc-ion battery
Zn storage mechanism
Zn-MnO2
Descripción
Sumario:Rechargeable aqueous zinc-ion batteries (AZIBs) have emerged as a leading contender for stationary energy storage systems due to their low cost, safety, and environmental sustainability. However, their widespread practical application is hindered by the limited stability and capacity of current AZIB cathodes, such as manganese oxide (MnO<inf>2</inf>), which affects their long-term cost-effectiveness. To overcome this limitation, we introduce zinc (Zn) doping in δ-MnO<inf>2</inf>, which modulates the electronic states of Mn atoms, suppresses Jahn–Teller distortion, and enhances structural stability. Additionally, the use of a binder-free, self-supported porous electrode without current collectors facilitates three-dimensional ion diffusion, further improving electrochemical performance. As a result, the assembled AZIBs demonstrate outstanding rate capability, delivering 440 mAh∙g<sup>-1</sup> at 0.2 A∙g<sup>-1</sup> and retaining 118 mAh∙g<sup>-1</sup> at 24 A∙g<sup>-1</sup> for Zn-doped δ-MnO<inf>2</inf>, outperforming the bare δ-MnO<inf>2</inf> with 356 mAh∙g<sup>-1</sup> at 0.2 A∙g<sup>-1</sup> and 80 mAh∙g<sup>-1</sup> at 24 A∙g<sup>-1</sup>. Additionally, the Zn-doped δ-MnO<inf>2</inf> exhibits excellent cycling performance with ∼100 % capacity retention after 6000 cycles at 150 mAh∙g<sup>-1</sup> at 10 A∙g<sup>-1</sup>. Furthermore, Zn-doped MnO<inf>2</inf> electrodes integrated with carbon nanotubes achieve a high capacity of ∼210 mAh∙g<sup>-1</sup>, even at an ultrahigh mass loading (∼20 mg∙cm<sup>-2</sup>) at 0.6 mA∙g<sup>-1</sup>. While energy storage in MnO<inf>2</inf> involves the reaction and insertion of H<sup>+</sup>, Mn<sup>2+</sup>, and Zn<sup>2+</sup> cations, density functional theory calculations reveal that Zn intercalation is the dominant storage mechanism in these cells. Overall, this study highlights the potential of Zn-doped MnO<inf>2</inf> cathodes as a promising strategy for advancing the stability, capacity, and rate performance of next-generation AZIBs.