Unraveling the Charge-Storage Mechanism in High-Performance Zinc-Ion Hybrid Supercapacitors

Abstract

The crucial request for alternative clean energy technologies to replace conventional fossil fuels and drive technological advancement in consumer and wearable electronics, electric vehicles etc. has led to great advancement in electrochemical energy storage systems research. The lithium-ion battery possesses high energy density while the supercapacitor can guarantee high power density. However, modern technologies such as integrated solar and wind energy solutions require a blend of high energy and power density devices, which is a great challenge. Presently, there is increased research interest in aqueous hybrid supercapacitors, a device capable of combining the high energy density of rechargeable batteries and the high-power density of electric-double layer capacitors.The current hotspot of the hybrid supercapacitor research is the zinc-ion hybrid supercapacitor owing to its several advantages such as the abundance of Zinc resource over lithium, high theoretical capacity of Zn, double charge transfer compared to univalent Lithium, environmental safety and high energy/power density. Wang et al first reported the carbon zinc-ion hybrid supercapacitor in 2018 by directly using zinc foil as anode and bio-carbon as cathode to realize long stability up to 20000 cycles. Next, Dong et al also developed an activated carbon-based zinc-ion hybrid supercapacitor which achieved a high energy density of ~84 Wh kg-1 and power density of 14.9 kW kg-1 in a potential window of 0.2 – 1.8 V. Despite the rapid advances over a short period in this class of energy storage devices, some problems still exist. The coulombic efficiency of Zinc-ion hybrid supercapacitors is inferior in low-cost ZnSO4 electrolytes owing to side reactions between the electrolyte and the Zn anode, while the mass loading of commonly used carbon cathode is extremely low (less than 2 mg cm-2). Importantly, the charge storage mechanism in zinc-ion hybrid supercapacitors is unclear.In this work, we developed high performance zinc-ion hybrid supercapacitors with superior charge storage, improved rate capability, and high power and energy density using a high mass density carbon anode with superior capacitive/pseudocapacitive storage. We successfully reveal that the charge storage of zinc-ion hybrid supercapacitors is extensively limited in zinc sulfate electrolytes and successfully address the coulombic efficiency problem using by modifying the electrolyte. Finally, using techniques such as in-situ Raman spectroscopy and X-ray diffraction analysis, we probe the charge storage mechanism and unravel a double cation charge storage mechanism, resulting in high energy density and extended potential window. Finally, our work provides crucial insights into understanding the charge storage process of zinc-ion hybrid supercapacitors and designing hybrid supercapacitors with new material chemistries.