Today's supercapacitor energy storages are typically discrete devices aimed for printed boards and power applications. The development of autonomous sensor networks and wearable electronics and the miniaturisation of mobile devices would benefit substantially from solutions in which the energy storage is integrated with the active device. Nanostructures based on porous silicon (PS) provide a route towards integration due to the very high inherent surface area to volume ratio and compatibility with microelectronics fabrication processes. Unfortunately, pristine PS has limited wettability and poor chemical stability in electrolytes and the high resistance of the PS matrix severely limits the power efficiency. In this work, we demonstrate that excellent wettability and electro-chemical properties in aqueous and organic electrolytes can be obtained by coating the PS matrix with an ultra-thin layer of titanium nitride by atomic layer deposition. Our approach leads to very high specific capacitance (15 Fcm -3 ), energy density (1.3 mWhcm -3 ) , p o w e r d e n s i t y ( u p t o 2 1 4 W c m -3 ) and excellent stability (more than 13,000 cycles). Furthermore, we show that the PS-TiN nanomaterial can be integrated inside a silicon chip monolithically by combining MEMS and nanofabrication techniques. This leads to realisation of in-chip supercapacitor, i.e., it opens a new way to exploit the otherwise inactive volume of a silicon chip to store energy.

Harvesting micropower energy from the ambient environment requires an intermediate energy storage, for which printed aqueous supercapacitors are well suited due to their low cost and environmental friendliness. In this work, a systematic study of a large set of devices is used to investigate the effect of process variability and operating voltage on the performance and stability of screen printed aqueous supercapacitors. The current collectors and active layers are printed with graphite and activated carbon inks, respectively, and aqueous NaCl used as the electrolyte. The devices are characterized through galvanostatic discharge measurements for quantitative determination of capacitance and equivalent series resistance (ESR), as well as impedance spectroscopy for a detailed study of the factors contributing to ESR. The capacitances are 200–360 mF and the ESRs 7.9–12.7 Ω, depending on the layer thicknesses. The ESR is found to be dominated by the resistance of the graphite current collectors and is compatible with applications in low-power distributed electronics. The effects of different operating voltages on the capacitance, leakage and aging rate of the supercapacitors are tested, and 1.0 V found to be the optimal choice for using the devices in energy harvesting applications.

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