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...
| Autores: | , , , , , , , , , , , , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/399225 |
| Acesso em linha: | http://hdl.handle.net/10261/399225 https://api.elsevier.com/content/abstract/scopus_id/105012221915 |
| Access Level: | acceso abierto |
| Palavra-chave: | Binder-free High-capacity retention Self-supporting electrode Zinc-ion battery Zn storage mechanism Zn-MnO2 |
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Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| title |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| spellingShingle |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage Chacón-Borrero, Jesús Binder-free High-capacity retention Self-supporting electrode Zinc-ion battery Zn storage mechanism Zn-MnO2 |
| title_short |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| title_full |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| title_fullStr |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| title_full_unstemmed |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| title_sort |
Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage |
| dc.creator.none.fl_str_mv |
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 |
| author |
Chacón-Borrero, Jesús |
| author_facet |
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 |
| author_role |
author |
| author2 |
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 |
| author2_role |
author author author author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) European Commission National Natural Science Foundation of China Natural Science Foundation of Guangdong Province National Research Council of Thailand China Scholarship Council Universidad Autónoma de Barcelona Generalitat de Catalunya ICREA Acadèmia Cabot, Andreu [0000-0002-7533-3251] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Binder-free High-capacity retention Self-supporting electrode Zinc-ion battery Zn storage mechanism Zn-MnO2 |
| topic |
Binder-free High-capacity retention Self-supporting electrode Zinc-ion battery Zn storage mechanism Zn-MnO2 |
| description |
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. |
| publishDate |
2025 |
| dc.date.none.fl_str_mv |
2025 2025 2025 |
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info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
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http://hdl.handle.net/10261/399225 https://api.elsevier.com/content/abstract/scopus_id/105012221915 |
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http://hdl.handle.net/10261/399225 https://api.elsevier.com/content/abstract/scopus_id/105012221915 |
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Inglés |
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Inglés |
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#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136883OB-C22 info:eu-repo/grantAgreement/EC/H2020/964524 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-149158OB-C43 info:eu-repo/grantAgreement/AEI//RED2022–134508-T info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021–001214-S info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-124572OB-C31 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2023–001300-M The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.ensm.2025.104486 https://doi.org/10.1016/j.ensm.2025.104486 Sí |
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Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storageChacón-Borrero, JesúsChang, XingqiMin, ZhiwenYu, JingMontaña-Mora, GuillemMejia-Centeno, Karol V.Sun, YuanmiaoZhou, XiaolongTunmee, SarayutKidkhunthod, PinitLi, JunshanLlorca, JordiArbiol, JordiCabot, AndreuBinder-freeHigh-capacity retentionSelf-supporting electrodeZinc-ion batteryZn storage mechanismZn-MnO2Rechargeable 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.This work was supported by the project SyDECat (PID2022–136883OB-C22), financed by the Spanish MCIN/AEI, EHAWEDRY (964524), financed by European EXCELLENT SCIENCE – Further and Emerging Technologies, the National Natural Science Foundation of China (52272054, 52125105, 52061160484, 51972329), Natural Science Foundation of Guangdong Province (2019TX05L389, 2022A1515011365), Shenzhen Science and Technology Planning Project (GJHZ20220913142809019, JCYJ20200109115624923), and the Foundation of the National Research Council of Thailand (N42A650253). Thanks to the China Scholarship Council (CSC) for the scholarship support. Part of the present work has been performed in the framework of the Universitat Autònoma de Barcelona Materials Science PhD program. ICN2 acknowledges funding from Generalitat de Catalunya 2021SGR00457. This study is part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat de Catalunya (In-CAEM Project). The authors thank support from the project AMaDE (PID2023–149158OB-C43), funded by MCIN/ AEI/10.13039/501100011033/ and by “ERDF A way of making Europe”, by the “European Union”. Grant RED2022–134508-T (CAT&SCALE) funded by MCIN/AEI /10.13039/501100011033. ICN2 is supported by the Severo Ochoa program from Spanish MCIN / AEI (Grant No.: CEX2021–001214-S) and is funded by the CERCA Programme / Generalitat de Catalunya. The authors acknowledge the use of instrumentation as well as the technical advice provided by the Joint Electron Microscopy Center at ALBA (JEMCA). ICN2 acknowledges funding from Grant IU16–014206 (METCAM-FIB) funded by the European Union through the European Regional Development Fund (ERDF), with the support of the Ministry of Research and Universities, Generalitat de Catalunya. ICN2 is a founding member of e-DREAM． [59] J.L. is a Serra Húnter Fellow and is grateful to the ICREA Academia program and projects MCIN/FEDER PID2021–124572OB-C31, CEX2023–001300-M, and GC 2021 SGR 01061.With funding from the Spanish government through the "Severo Ochoa Centre of Excelence" accreditation (CEX2021–001214-S)With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (CEX2023–001300-M)Peer reviewedElsevierMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)European CommissionNational Natural Science Foundation of ChinaNatural Science Foundation of Guangdong ProvinceNational Research Council of ThailandChina Scholarship CouncilUniversidad Autónoma de BarcelonaGeneralitat de CatalunyaICREA AcadèmiaCabot, Andreu [0000-0002-7533-3251]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/399225https://api.elsevier.com/content/abstract/scopus_id/105012221915reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136883OB-C22info:eu-repo/grantAgreement/EC/H2020/964524info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-149158OB-C43info:eu-repo/grantAgreement/AEI//RED2022–134508-Tinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021–001214-Sinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-124572OB-C31info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2023–001300-MThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.ensm.2025.104486https://doi.org/10.1016/j.ensm.2025.104486Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3992252026-05-22T06:33:51Z |
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15,812429 |