Carbon Nanocluster-Mediated Nanoblending Assembly for Binder-Free Energy Storage Electrodes with High Capacities and Enhanced Charge Transfer Kinetics.

The effective spatial distribution and arrangement of electrochemically active and conductive components within metal oxide nanoparticle (MO NP)-based electrodes significantly impact their energy storage performance. Unfortunately, conventional electrode preparation processes have much difficulty addressing this issue. Herein, this work demonstrates that a unique nanoblending assembly based on favorable and direct interfacial interactions between high-energy MO NPs and interface-modified carbon nanoclusters (CNs) notably enhances the capacities and charge transfer kinetics of binder-free electrodes in lithium-ion batteries (LIBs). For this study, carboxylic acid (COOH)-functionalized carbon nanoclusters (CCNs) are consecutively assembled with bulky ligand-stabilized MO NPs through ligand-exchange-induced multidentate binding between the COOH groups of CCNs and the surface of NPs. This nanoblending assembly homogeneously distributes conductive CCNs within densely packed MO NP arrays without insulating organics (i.e., polymeric binders and/or ligands) and prevents the aggregation/segregation of electrode components, thus markedly reducing contact resistance between neighboring NPs. Furthermore, when these CCN-mediated MO NP electrodes are formed on highly porous fibril-type current collectors (FCCs) for LIB electrodes, they deliver outstanding areal performance, which can be further improved through simple multistacking. The findings provide a basis for better understanding the relationship between interfacial interaction/structures and charge transfer processes and for developing high-performance energy storage electrodes.

High-performance electrified hydrogel actuators based on wrinkled nanomembrane electrodes for untethered insect-scale soft aquabots.

Hydrogels have diverse chemical properties and can exhibit reversibly large mechanical deformations in response to external stimuli; these characteristics suggest that hydrogels are promising materials for soft robots. However, reported actuators based on hydrogels generally suffer from slow response speed and/or poor controllability due to intrinsic material limitations and electrode fabrication technologies. Here, we report a hydrogel actuator that operates at low voltages (<3 volts) with high performance (strain > 50%, energy density > 7 × 105 joules per cubic meter, and power density > 3 × 104 watts per cubic meter), surpassing existing hydrogel actuators and other types of electroactive soft actuators. The enhanced performance of our actuator is due to the formation of wrinkled nanomembrane electrodes that exhibit high conductivity and excellent mechanical deformation through capillary-assisted assembly of metal nanoparticles and deswelling-induced wrinkled structures. By applying an electric potential through the wrinkled nanomembrane electrodes that sandwich the hydrogel, we were able to trigger a reversible and substantial electroosmotic water flow inside a hydrogel film, which drove the controlled swelling of the hydrogel. The high energy efficiency and power density of our wrinkled nanomembrane electrode-induced actuator enabled the fabrication of an untethered insect-scale aquabot integrated with an on-board control unit demonstrating maneuverability with fast locomotion speed (1.02 body length per second), which occupies only 2% of the total mass of the robot.

A Layer-by-Layer Assembly Route to Electroplated Fibril-Based 3D Porous Current Collectors for Energy Storage Devices.

Electrical conductivity, mechanical flexibility, and large electroactive surface areas are the most important factors in determining the performance of various flexible electrodes in energy storage devices. Herein, a layer-by-layer (LbL) assembly-induced metal electrodeposition approach is introduced to prepare a variety of highly porous 3D-current collectors with high flexibility, metallic conductivity, and large surface area. In this study, a few metal nanoparticle (NP) layers are LbL-assembled onto insulating paper for the preparation of conductive paper. Subsequent Ni electroplating of the metal NP-coated substrates reduces the sheet resistance from ≈103 to <0.1 Ω sq-1 while maintaining the porous structure of the pristine paper. Particularly, this approach is completely compatible with commercial electroplating processes, and thus can be directly extended to electroplating applications using a variety of other metals in addition to Ni. After depositing high-energy MnO NPs onto Ni-electroplated papers, the areal capacitance increases from 68 to 811 mF cm-2 as the mass loading of MnO NPs increases from 0.16 to 4.31 mg cm-2 . When metal NPs are periodically LbL-assembled with the MnO NPs, the areal capacitance increases to 1710 mF cm-2 .

Interfacial control and design of conductive nanomaterials for transparent nanocomposite electrodes.

A few critical issues in preparing transparent conductive electrodes (TCEs) based on solution-processable conductive nanomaterials are their low electrical conductivity and the unfavorable trade-off between electrical conductivity and optical transparency, which are closely related to the organic ligands bound to the nanomaterial surface. In particular, bulky/insulating organic ligands bound to the surface of conductive nanomaterials unavoidably act as high contact resistance sites at the interfaces between neighboring nanomaterials, which adversely affects the charge transfer kinetics of the resultant TCEs. This article reviews the latest research status of various interfacial control approaches for solution-processable TCEs. We describe how these approaches can be effectively applied to conductive nanomaterials and how interface-controlled conductive nanomaterials can be employed to improve the electrical and/or electrochemical performance of various transparent nanocomposite electrodes, including TCEs, energy storage electrodes, and electrochromic electrodes. Last, we provide perspectives on the development direction for next-generation transparent nanocomposite electrodes and breakthroughs for significantly mitigating the complex trade-off between their electrical/electrochemical performance and optical transparency.

Electroosmosis-Driven Hydrogel Actuators Using Hydrophobic/Hydrophilic Layer-By-Layer Assembly-Induced Crack Electrodes.

Development of soft actuators with higher performance and more versatile controllability has been strongly required for further innovative advancement of various soft applications. Among various soft actuators, electrochemical actuators have attracted much attention due to their lightweight, simple device configuration, and facile low-voltage control. However, the reported performances have not been satisfactory because their working mechanism depends on the limited electrode expansion by conventional electrochemical reactions. Herein, we report an electroosmosis-driven hydrogel actuator with a fully soft monolithic structure-based whole-body actuation mechanism using an amphiphilic interaction-induced layer-by-layer assembly. For this study, cracked electrodes with interconnected metal nanoparticles are prepared on hydrogels through layer-by-layer assembly and shape transformation of metal nanoparticles at hydrophobic/hydrophilic solvent interfaces. Electroosmotic pumping by cracked electrodes instantaneously induces hydrogel swelling through reversible and substantial hydraulic flow. The resultant actuator exhibits actuation strain of higher than 20% and energy density of 1.06 × 105 J m-3, allowing various geometries (e.g., curved-planar and square-pillared structures) and motions (e.g., slow-relaxation, spring-out, and two degree of freedom bending). In particular, the energy density of our actuators shows about 10-fold improvement than those of skeletal muscle, electrochemical actuators, and various stimuli-responsive hydrogel actuators reported to date.

Layer-by-Layer Assembled Oxide Nanoparticle Electrodes with High Transparency, Electrical Conductivity, and Electrochemical Activity by Reducing Organic Linker-Induced Oxygen Vacancies.

Solution-processable transparent conducting oxide (TCO) nanoparticle (NP)-based electrodes are limited by their low electrical conductivity, which originates from the low level of oxygen vacancies within NPs and the contact resistance between neighboring NPs. Additionally, these electrodes suffer from the troublesome trade-off between electrical conductivity and optical transmittance and the restricted shape of substrates (i.e., only flat substrates). An oxygen-vacancy-controlled indium tin oxide (ITO) NP-based electrode is introduced using carbon-free molecular linkers with strong chemically reducing properties. Specifically, ITO NPs are layer-by-layer assembled with extremely small hydrazine monohydrate linkers composed of two amine groups, followed by thermal annealing. This approach markedly improves the electrical conductivity of ITO NP-based electrodes by significantly increasing the level of oxygen vacancies and decreasing the interparticle distance (i.e., contact resistance) without sacrificing optical transmittance. The prepared electrodes surpass the optical/electrical performance of TCO NP-based electrodes reported to date. Additionally, the nanostructured ITO NP films can be applied to more complex geometric substrates beyond flat substrates, and furthermore exhibit a prominent electrochemical activity. This approach can provide an important basis for developing a wide range of highly functional transparent conducting electrodes.

A Metal-Like Conductive Elastomer with a Hierarchical Wrinkled Structure.

For the development of wearable electronics, the replacement of rigid, metallic components with fully elastomeric materials is crucial. However, current elastomeric electrodes suffer from low electrical conductivity and poor electrical stability. Herein, a metal-like conductive elastomer with exceptional electrical performance and stability is presented, which is used to fabricate fully elastomeric electronics. The key feature of this material is its wrinkled structure, which is induced by in situ cooperation of solvent swelling and densely packed nanoparticle assembly. Specifically, layer-by-layer assembly of metal nanoparticles and small-molecule linkers on elastomers generates the hierarchical wrinkled elastomer. The elastomer demonstrates remarkable electrical conductivity (170 000 and 11 000 S cm-1 at 0% and 100% strain, respectively), outperforming previously reported elastomeric electrodes based on nanomaterials. Furthermore, a fully elastomeric triboelectric nanogenerator based on wrinkled elastomeric electrode exhibits excellent electric power generation performance due to the compressible, large contact area of the wrinkled surface during periodic contact and separation.

High-performance electrochromic films with fast switching times using transparent/conductive nanoparticle-modulated charge transfer.

One of the most critical issues in electrochromic (EC) films based on transition metal oxides such as tungsten oxides (WOx) is their poor charge transfer property, which is closely related to EC performance. Herein, high-performance EC films with enhanced charge transport are prepared using small-molecule linkers and transparent/conductive nanoparticles (NPs). In this work, oleylamine (OAm)-stabilized WO2.72 nanorods (NRs) and OAm-stabilized indium tin oxide (ITO) NPs are layer-by-layer (LbL)-assembled with small-molecule linkers (tris(2-aminoethyl)amine, TREN) using a ligand-exchange reaction between bulky/insulating OAm ligands and TREN molecules. In this case, there is only one TREN layer between neighboring inorganic components (WO2.72 NRs and/or ITO NPs), resulting in a dramatic decrease in the separation distance. This minimized separation distance as well as the periodic insertion of transparent/conductive ITO NPs can significantly reduce the charge transfer resistance within WO2.72 NR-based EC films, which remarkably improves their EC performance. Compared to EC films without ITO NPs, the formed EC films with ITO NPs exhibit faster switching responses (4.1 times in coloration time and 3.5 times in bleaching time) and a maximum optical modulation of approximately 55.8%. These results suggest that electrochemical performance, including EC performance, can be significantly improved through structural/interfacial designing of nanocomposites.