Reversible surface reconstruction of Na3NiCO3PO4: A battery type electrode for pseudocapacitor applications.

Recently, a new class of mixed polyanionic compounds with general formula Na 3 MPO 4 CO 3 (M = Ni, Mn, Fe, Co, Cu), discovered through high-throughput computations have attracted much attention for its secondary battery applications and safety aspects. Here, we combine electrochemical measurements with inductively coupled plasma-optical emission spectrometer (ICP-OES), energy-dispersive X-ray (EDX), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), and an ab-initio DFT approach to unravel the dynamic self-limiting surface restructuring of Na 3 NiCO 3 PO 4 in aqueous 1 M KOH/NaOH electrolyte. The etching of lattice CO 3 2-, PO 4 3- and Na serves as the key to trigger the surface reconstruction. This work establishes a fundamental understanding of the pseudocapacitance mechanism associated with surface self-reconstruction of mixed polyanionic compounds. The reconstruction-derived self-limiting dense Ni(OH) 2 layers at the surface and its oxidation to NiOOH at anodic potentials can be attributed to the observed high-performance pseudocapacitive behavior. The surface reconstructed Na 3 NiCO 3 PO 4 electrode exhibits high specific capacitance (2378.2 F g−1 at 1 A g−1). The assembled symmetric pseudocapacitor delivers a high energy density (57.2 Wh kg−1), power density (1500 W kg−1) at 1 Ag-1 and long cycle life (13000 cycles) with 100% retention. [Display omitted] • The pseudocapacitive behavior of the Na 3 NiCO 3 PO 4 is tested. • The Na 3 NiCO 3 PO 4 undergo surface self-reconstruction. • The etching of lattice CO 3 2-, PO 4 3- and Na lead to the formation of Ni(OH) 2 at the surface. • The electrode exhibits high specific capacitance 2378.2 F g−1 at 1 A g−1 • The assembled device delivers a high energy density, power density and long cycle life. [ABSTRACT FROM AUTHOR]