All‐Electrochemical Nanofabrication of Stacked Ternary Metal Sulfide/Graphene Electrodes for High‐Performance Alkaline Batteries

Energy-storage materials can be assembled directly on the electrodes of a battery using electrochemical methods, this allowing sequential deposition, high structural control, and low cost. Here, a two-step approach combining electrophoretic deposition (EPD) and cathodic electrodeposition (CED) is demonstrated to fabricate multilayer hierarchical electrodes of reduced graphene oxide (rGO) and mixed transition metal sulfides (NiCoMnSx). The process is performed directly on conductive electrodes applying a small electric bias to electro-deposit rGO and NiCoMnSx in alternated cycles, yielding an ideal porous network and a continuous path for transport of ions and electrons. A fully rechargeable alkaline battery (RAB) assembled with such electrodes gives maximum energy density of 97.2 Wh kg−1 and maximum power density of 3.1 kW kg−1, calculated on the total mass of active materials, and outstanding cycling stability (retention 72% after 7000 charge/discharge cycles at 10 A g−1). When the total electrode mass of the cell is considered, the authors achieve an unprecedented gravimetric energy density of 68.5 Wh kg−1, sevenfold higher than that of typical commercial supercapacitors, higher than that of Ni/Cd or lead–acid Batteries and similar to Ni–MH Batteries. The approach can be used to assemble multilayer composite structures on arbitrary electrode shapes.