Ordered Vacancies as Sodium Ion Micropumps in Cu-Deficient Copper Indium Diselenide to Enhance Sodium Storage.

Unordered vacancies engineered in host anode materials cannot well maintain the uniform Na adsorbed and possibly render the local structural stress intense, resulting in electrode peeling and battery failure. Here, the indium is first introduced into CuSe to achieve the formation of CuInSe. Next, an ion extraction strategy is employed to fabricate CuInSe enriched with ordered vacancies by spontaneous formation of defect pairs. Such ordered defects, compared with unordered ones, can serve as myriad sodium ion micropumps evenly distributing in crystalline host to homogenize the adsorbed Na and the generated volumetric stress during the electrochemistry. Furthermore, CuInSe is indeed proved by the calculations to exhibit smaller volumetric variation than the counterpart with unordered vacancies. Thanks to the distinct ordered vacancy structure, the material exhibits a highly reversible capacity of 428 mAh g at 1 C and a high-rate stability of 311.7 mAh g at 10 C after 5000 cycles when employed as an anode material for Sodium-ion batteries (SIBs). This work presents the promotive effect of ordered vacancies on the electrochemistry of SIBs and demonstrates the superiority to unordered vacancies, which is expected to extend it to other metal-ion batteries, not limited to SIBs to achieve high capacity and cycling stability.