Ion‐Diode‐Like Heterojunction for Improving Electricity Generation from Water Droplets by Capillary Infiltration

Abstract Water‐droplet‐based electricity generators are emerging hydrovoltaic technologies that harvest energy from water circulation through strong interactions between water and nanomaterials. However, such devices exhibit poor current performance owing to their unclear driving force (evaporation or infiltration) and undesirable reverse diffusion current. Herein, a water‐droplet‐based hydrovoltaic electricity generator induced by capillary infiltration with an asymmetric structure composed of a diode‐like heterojunction formed by negatively and positively charged materials is fabricated. This device can generate current densities of 160 and 450 µA cm⁻² at room temperature and 65 °C, respectively. The heterojunction achieves a rectification ratio of 12, which effectively suppresses the reverse current caused by concentration differences. This results in an improved charge accumulation of ≈60 mC cm⁻² in 1000 s, which is three times the value observed in the control device. When the area of the device is increased to 6 cm², the current increases linearly to 1 mA, thus demonstrating the scale‐up potential of the generator. It has been proven that the streaming potential originates from capillary infiltration, and the presence of ion rectification. The proposed method of constructing ion‐diode‐like structures provides a new strategy for improving generator performance.