Phase-Dependent Energy Storage Performance of the NixSey Polymorphs for Supercapacitor-Battery Hybrid Devices

Transition-metal chalcogenides have emerged as a promising class of materials for energy storage applications due to their earth abundance, high theoretical capacity, and high electrical conductivity. Herein, we introduce a facile and one-pot electrodeposition method to prepare high-performance nickel selenide Ni_xSe_y (0.5 ≤ x/y ≤ 1.5) nanostructures (specific capacity = 180.3 mA h g^-1 at 1 A g^-1). The as-synthesized nickel selenide (NS) nanostructure is however converted to other polymorphs of nickel selenide including orthorhombic NiSe₂, trigonal Ni₃Se₂, hexagonal NiSe, and orthorhombic Ni₆Se₅ over cycling. Interestingly, NiSe₂ and Ni₃Se₂ polymorphs that display a more metallic character and superior energy storage performance are the predominant phases after a few hundred cycles. We fabricated a hybrid device using activated carbon (AC) as a supercapacitor-type negative electrode and NS as a high-rate battery-type positive electrode (AC||NS). This hybrid device provides a high specific energy of 71 W h kg^-1, an excellent specific power of up to 31 400 W kg^-1, and exceptional cycling stability (80% retention of the initial capacity after 20 000 cycles). The higher energy storage performance of the device is a result of the development of high-performance NiSe₂ and Ni₃Se₂ polymorphs. Moreover, the reduction of the critical dimension of the NS particles to the nanoscale partially induces an extrinsic pseudocapacitive behavior that improves the rate capability and durability of the device. We also explored the origin of the superior energy storage performance of the NS polymorphs using density functional theory calculations in terms of the computed density of states around the Fermi level, electrical conductivity, and quantum capacitance that follows the trend NiSe₂ > Ni₃Se₂ > NiSe > Ni₆Se₅. The present study thus provides an appealing approach for tailoring the phase composition of NS as an alternative to the commonly used templated synthesis methods.