Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage

Abstract Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency, which motivates ardent pursuing on the synthetic approaches of hollow materials. Herein, an...

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Main Authors: Jiamin Fei, Shiqiang Zhao, Xiaoxu Bo, Furong Xie, Guanghui Li, Ebrahim‐Alkhalil M. A. Ahmed, Qingcheng Zhang, Huile Jin, Zhiqun Lin
Format: Article
Language:English
Published: Wiley 2023-08-01
Series:Carbon Energy
Subjects:
Online Access:https://doi.org/10.1002/cey2.333
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author Jiamin Fei
Shiqiang Zhao
Xiaoxu Bo
Furong Xie
Guanghui Li
Ebrahim‐Alkhalil M. A. Ahmed
Qingcheng Zhang
Huile Jin
Zhiqun Lin
author_facet Jiamin Fei
Shiqiang Zhao
Xiaoxu Bo
Furong Xie
Guanghui Li
Ebrahim‐Alkhalil M. A. Ahmed
Qingcheng Zhang
Huile Jin
Zhiqun Lin
author_sort Jiamin Fei
collection DOAJ
description Abstract Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency, which motivates ardent pursuing on the synthetic approaches of hollow materials. Herein, an intriguing route, combining solid precursor transition and Ostwald ripening (SPTOR), is developed to craft nano single‐crystal (SC)‐constructed MnCO3 submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix (MnCO3 SMHSs/rGO). It is noteworthy that the H‐bonding interaction between Mn3O4 nanoparticles (NPs) and oxygen‐containing groups on GO promotes uniform anchoring of Mn3O4 NPs on GO, mild reductant ascorbic acid triggers the progressive solid‐to‐solid transition from Mn3O4 NPs to MnCO3 submicron solid spindles (SMSSs) in situ on GO, and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO3 SMSSs and subsequent recrystallization on surface SCs of MnCO3 SMHSs. Remarkably, MnCO3 SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g−1 at 1000 mA g−1, which is 10 times higher than that of MnCO3 microspheres/rGO fabricated from a conventional Mn2+ salt precursor (202 mAh g−1). The ultrahigh capacity and ultralong lifespan of MnCO3 SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability, enabled by the fast ion/electron transfer, large specific surface area, and robust electrode pulverization inhibition efficacy. Moreover, fascinating in‐depth lithium storage reactions of MnCO3 are observed such as the oxidation of Mn2+ in MnCO3 to Mn3+ in charge process after long‐term cycles and the further lithiation of Li2CO3 in discharge process. As such, the SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.
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spelling doaj.art-8d32b63128124b118110b1c5a76a96412023-08-28T08:53:45ZengWileyCarbon Energy2637-93682023-08-0158n/an/a10.1002/cey2.333Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storageJiamin Fei0Shiqiang Zhao1Xiaoxu Bo2Furong Xie3Guanghui Li4Ebrahim‐Alkhalil M. A. Ahmed5Qingcheng Zhang6Huile Jin7Zhiqun Lin8Zhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaZhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering Wenzhou University Wenzhou ChinaDepartment of Chemical and Biomolecular Engineering National University of Singapore Singapore SingaporeAbstract Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency, which motivates ardent pursuing on the synthetic approaches of hollow materials. Herein, an intriguing route, combining solid precursor transition and Ostwald ripening (SPTOR), is developed to craft nano single‐crystal (SC)‐constructed MnCO3 submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix (MnCO3 SMHSs/rGO). It is noteworthy that the H‐bonding interaction between Mn3O4 nanoparticles (NPs) and oxygen‐containing groups on GO promotes uniform anchoring of Mn3O4 NPs on GO, mild reductant ascorbic acid triggers the progressive solid‐to‐solid transition from Mn3O4 NPs to MnCO3 submicron solid spindles (SMSSs) in situ on GO, and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO3 SMSSs and subsequent recrystallization on surface SCs of MnCO3 SMHSs. Remarkably, MnCO3 SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g−1 at 1000 mA g−1, which is 10 times higher than that of MnCO3 microspheres/rGO fabricated from a conventional Mn2+ salt precursor (202 mAh g−1). The ultrahigh capacity and ultralong lifespan of MnCO3 SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability, enabled by the fast ion/electron transfer, large specific surface area, and robust electrode pulverization inhibition efficacy. Moreover, fascinating in‐depth lithium storage reactions of MnCO3 are observed such as the oxidation of Mn2+ in MnCO3 to Mn3+ in charge process after long‐term cycles and the further lithiation of Li2CO3 in discharge process. As such, the SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.https://doi.org/10.1002/cey2.333hollow structureinterfacial and capacitive lithium storagelithium‐ion batteryMnCO3Ostwald ripeningsolid precursor transition
spellingShingle Jiamin Fei
Shiqiang Zhao
Xiaoxu Bo
Furong Xie
Guanghui Li
Ebrahim‐Alkhalil M. A. Ahmed
Qingcheng Zhang
Huile Jin
Zhiqun Lin
Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
Carbon Energy
hollow structure
interfacial and capacitive lithium storage
lithium‐ion battery
MnCO3
Ostwald ripening
solid precursor transition
title Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
title_full Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
title_fullStr Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
title_full_unstemmed Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
title_short Nano‐single‐crystal‐constructed submicron MnCO3 hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
title_sort nano single crystal constructed submicron mnco3 hollow spindles enabled by solid precursor transition combined ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
topic hollow structure
interfacial and capacitive lithium storage
lithium‐ion battery
MnCO3
Ostwald ripening
solid precursor transition
url https://doi.org/10.1002/cey2.333
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