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.

Tin dioxide (SnO2) has been widely implemented as an advanced anode material for lithium or sodium ion batteries (LIBs/SIBs) owing to the high capacity and moderate potential. However, conventional synthetic...