Calcium ion batteries (CIBs) are a promising energy storage device due to the low redox potential of the Ca metal and the abundant reserves of the Ca element. However, the large radius and divalent nature of Ca2+ lead to its slow ion diffusion kinetics and the lack of suitable electrode materials for Ca storage. Here, a layered structure of Na2Ti3O7 (NTO) is presented as an anode material for nonaqueous CIBs. This NTO anode demonstrates a high discharge capacity of 165 mA h g-1 at 100 mA g-1 and a remarkable capacity retention rate of 80%, even after 2000 cycles at 500 mA g-1, surpassing the performance of all reported intercalation-type anode materials for CIBs. The NTO transfers to layered CaVIINaIXTi3O7 (CNTO) with intercalation of Ca2+ and extraction of Na+ during the first discharge process. Then, the CNTO undergoes the reversible insertion/extraction of Ca2+ during subsequent cycling. Additionally, density functional theory calculations reveal that NTO possesses a rapid two-dimensional diffusion pathway for Ca2+. Moreover, the full CIBs based on NTO as the anode further underscore its potential for CIBs. This work presents promising anode materials for CIBs, offering opportunities to promote the development of high-performance CIBs.
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