Preaddition of Cations to Electrolytes for Aqueous 2.2 V High Voltage Hybrid Supercapacitor with Superlong Cycling Life and Its Energy Storage Mechanism

Electrolyte solutions and electrode active materials, as core components of energy storage devices, have a great impact on the overall performance. Currently, supercapacitors suffer from the drawbacks of low energy density and poor cyclic stability in typical alkaline aqueous electrolytes. Herein, the ultrathin Co₃O₄ anode material is synthesized by a facile electrodeposition, followed by postheat treatment process. It is found that the decomposition of active materials induces reduction of energy density and specific capacitance during electrochemical testing. Therefore, a new strategy of preadding Co²⁺ cations to achieve the dissolution equilibrium of cobalt in active materials is proposed, which can improve the cyclic lifetime of electrode materials and broaden the operation window of electrochemical devices. Co²⁺ and Li⁺ embedded in carbon electrode during charging can enhance H⁺ desorption energy barrier, further hampering the critical step of bulk water electrolysis. More importantly, the highly reversible chemical conversion mechanism between Co₃O₄ and protons is demonstrated to be the fact that a large amount of quantum dots and second-order flaky CoO layers were in situ formed in the electrochemical reaction process, which is first discovered and reported in neutral solutions. The as-assembled device achieves a high operation voltage (2.2 V), excellent cycling stability (capacitance retention of 168% after 10 000 cycles) and ultrahigh energy density (99 W h kg^-1 at a power density of 1100 W kg^-1). The as-prepared electrolytes and highly active electrode materials will open up new opportunities for aqueous supercapacitors with high safety, high voltage, high energy density, and long-lifespan.