Increasing insertion host materials are developed as high-performance anodes of “rocking-chair” zinc ion batteries. However, most of them show unsatisfactory rate capabilities. Herein, layered BiOIO3 is reported as an excellent insertion host and a zinc ion conductor, i.e., Zn3(PO4)2·4H2O (ZPO), is introduced to construct a BiOIO3@ZPO heterojunction with a built-in electric field (BEF). Both ZPO and a BEF obviously enhance Zn2+ transfer and storage, which is proven by theoretical calculations and experimental studies. The conversion-type mechanism of BiOIO3 is revealed through ex situ characterizations. The optimized electrode exhibits a high reversible capacity of 130 mAh g–1 at 0.1 A g–1, a low average discharge voltage of 0.58 V, an ultrahigh rate performance with 68 mAh g–1 at 5 A g–1 (52% of capacity at 0.1 A g–1), and an ultralong cyclic life of 6000 cycles at 5 A g–1. Significantly, the BiOIO3@ZPO//Mn3O4 full cell shows a good cyclic life of 67 mAh g–1 over 1000 cycles at 0.1 A g–1. This work provides a new insight into the design of anodes with excellent rate capability.

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