Nano‐single‐crystal‐constructed submicron MnCO<sub>3</sub> hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage
Jiamin Fei, Shiqiang Zhao, Xiaoxu Bo, Furong Xie, Guanghui Li, Ebrahim‐Alkhalil M. A. Ahmed, Qingcheng Zhang, Huile Jin, Zhiqun Lin
Abstract
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 MnCO 3 submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix (MnCO 3 SMHSs/rGO). It is noteworthy that the H‐bonding interaction between Mn 3 O 4 nanoparticles (NPs) and oxygen‐containing groups on GO promotes uniform anchoring of Mn 3 O 4 NPs on GO, mild reductant ascorbic acid triggers the progressive solid‐to‐solid transition from Mn 3 O 4 NPs to MnCO 3 submicron solid spindles (SMSSs) in situ on GO, and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO 3 SMSSs and subsequent recrystallization on surface SCs of MnCO 3 SMHSs. Remarkably, MnCO 3 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 MnCO 3 microspheres/rGO fabricated from a conventional Mn 2+ salt precursor (202 mAh g −1 ). The ultrahigh capacity and ultralong lifespan of MnCO 3 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 MnCO 3 are observed such as the oxidation of Mn 2+ in MnCO 3 to Mn 3+ in charge process after long‐term cycles and the further lithiation of Li 2 CO 3 in discharge process. As such, the SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.