Organic/Inorganic Hybrid Nanochannels Based on Polypyrrole‐Embedded Alumina Nanopore Arrays: pH‐ and Light‐Modulated Ion Transport

Inspired by the asymmetric structure and responsive ion transport in biological ion channels, organic/inorganic hybrid artificial nanochannels exhibiting pH‐modulated ion rectification and light‐regulated ion flux have been constructed by introducing conductive polymer into porous nanochannels. The hybrid nanochannels are achieved by partially modifying alumina (Al₂O₃) nanopore arrays with polypyrrole (PPy) layer using electrochemical polymerization, which results in an asymmetric component distribution. The protonation and deprotonation of Al₂O₃ and PPy upon pH variation break the surface charge continuity, which contributes to the pH‐tunable ion rectification. The ionic current rectification ratio is affected substantially by the pH value of electrolyte and the pore size of nanochannels. Furthermore, the holes (positive charges) in PPy layer induced by the cooperative effect of light and protons are used to regulate the ionic flux through the nanochannels, which results in a light‐responsive ion current. The magnitude of responsive ionic current could be amplified by optimizing this cooperation. This new type of stimuli‐responsive PPy/Al₂O₃ hybrid nanochannels features advantages of unique optical and electric properties from conducting PPy and high mechanical performance from porous Al₂O₃ membrane, which provide a platform for creating smart nanochannels system.     

Ionic Current Rectification in Soft‐Matter Diodes with Liquid‐Metal Electrodes

A soft‐matter‐based diode composed of hydrogel and liquid metal (eutectic gallium indium, EGaIn) is presented. The ability to control the thickness, and thus resistivity, of an oxide skin on the metal enables rectification. First, a simple model system with liquid‐metal/electrolyte‐solution/Pt interfaces is characterized. The electrically insulating oxide skin on the EGaIn electrode is reduced or oxidized further depending on the direction of the bias, thereby allowing unidirectional ionic current. The forward current of the diode increases as the conductivity of the electrolyte increases, whereas backward current depends on the pH of the medium in contact with the insulating oxide layer on the EGaIn electrode. As a result, the diode shows a higher rectification ratio (defined as the ratio of forward to backward current measured at the same absolute bias) with more conductive electrolyte at neutral pH. Replacement of the liquid electrolyte solution with a hydrogel improves the structural stability of the soft diode. The rectification performance also improves due to the increased ionic conductivity by the gel. Finally, a diode composed entirely of soft materials by replacing the platinum electrode with a second liquid‐metal electrode is presented. Contacting each liquid metal with a polyelectrolyte gel featuring different pH values provided asymmetry in the device, which is necessary for rectification. A hydrogel layer infused with a strong basic polyelectrolyte removes the insulating oxide layer, allowing one interface with the EGaIn electrode to be conductive regardless of the direction of bias. Thus, the oxide layer at the other interface rectifies the current.     

Multifunctional Electrode Design Consisting of 3D Porous Separator Modulated with Patterned Anode for High‐Performance Dual‐Ion Batteries

Searching for low‐cost and high‐capacity electrode materials such as metal anodes is of important significance for the development of new generation rechargeable batteries. However, metal anodes always suffer from severe volume expansion/contraction during a repeated electrochemical alloying/dealloying process. In this study, a novel concept about modifying metal‐anodes‐based battery construction with a multifunctional electrode (ME) design is provided. The ME consists of a 3D porous separator that is modulated with a patterned aluminum anode, which simultaneously works as a current collector, anode material, and separator in a dual‐ion battery (DIB). The 3D porous separator not only enables the ME to possess significantly improved electrolyte uptake and retention capabilities, but also acts as a protecting layer to restrict the surface pulverization of the Al anode. The ME‐DIB displays remarkably enhanced cell performances, including excellent cycling stability with 92.4% capacity retention after 1000 cycles at a current density of 2 C, and superior rate performance with 80.7% capacity retention at 10 C.